Probing the conformation of polyelectrolytes in mesoporous silica spheres

We report a fluorescence-based approach to probing the conformation of a macromolecule, poly(allylamine hydrochloride) (PAH), in bimodal mesoporous silica (BMS) particles. The method involves monitoring the fluorescent properties of the probe, 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt (4-PSA), upon electrostatic binding to PAH molecules adsorbed in the nanopores of the BMS particles. PAH infiltration into the BMS particles, quantified by thermogravimetric analysis and visualized by confocal laser scanning microscopy, was examined as a function of PAH adsorption time, PAH molecular weight, and the sodium chloride (NaCl) concentration and pH of the PAH adsorption solution. The conformation of PAH molecules in the nanopores was investigated by incubating the PAH-loaded BMS particles in 4-PSA and using the ratio of the excimer to monomer emission intensity to discern differences in the PAH conformation in the nanopores. Control experiments involving nonporous silica (NS) particles were also conducted to determine the extent to which the nanopores within the BMS particles influence the degree of PAH adsorption and the conformation of the adsorbed PAH molecules. The data indicate that PAH molecules adsorbed in the nanopores adopt a more coiled conformation than PAH molecules adsorbed on NS particles over a wide range of conditions. Further, the conformation of PAH molecules in the nanopores can be tuned by adjusting the NaCl concentration and/or pH of the PAH adsorption solution. 4-PSA titration experiments revealed that at saturation binding there are ca. 3.8 PAH monomer units per 4-PSA molecule. This study provides insights into macromolecule infiltration and conformation in nanopores, which are important for the application of mesoporous materials in the fields of adsorption/immobilization, catalysis, delivery, sensing, separations, and synthesis.     

The Application of Perdeuterated Polycyclic Aromatic Hydrocarbons (PAH) as Internal Standards for the Liquid Chromatographic Determination of PAH in a Petroleum Crude Oil and Other Complex Mixtures

Abstract

A sequential liquid chromatographic (LC) procedure for the determination of polycyclic aromatic hydrocarbons (PAH) in a petroleum crude oil and other complex mixtures is described. The procedure includes normal-phase LC on an aminosilane column to isolate fractions containing isomeric PAH and reversed-phase LC on a polymeric C₁₈ column to separate the individual PAH isomers. Appropriate perdeuterated PAH are added to the sample so that each isomeric fraction will contain one internal standard. The perdeuterated PAH are excellent internal standards for this sequential LC procedure. Perdeuterated PAH have normal-phase and reversed-phase LC retention characteristics similar to those of the parent PAH. In the normal-phase LC separation, the perdeuterated PAH elute in the same fraction as the parent PAH. In the reversed-phase LC separation, the perdeuterated PAH elute first and are generally resolved from the parent PAH. The optimized spectrofluorometric detection of each PAH analyte is accomplished by programming appropriate sets of excitation and emission wavelengths to correspond with the elation time of each analyte on the polymeric C₁₈ column. The analytical results obtained from this procedure for the analysis of a shale oil sample [Standard Reference Material (SRM) 1580] and a petroleum crude oil (SRM 1582) are compared to values obtained by gas chromatography - mass spectrometry.     

Differentiation of isomeric polyaromatic hydrocarbons by electrospray Ag(I) cationization mass spectrometry

Abundant Ag(I)-cationized complexes of 13 polyaromatic hydrocarbons (PAHs), [Ag+PAH](+) and [Ag+2(PAH)](+), were readily generated by electrospray ionization (ESI). In-source collision-induced dissociation (CID) of the [Ag+2(PAH)](+) complex yielded the monomer complex [Ag+PAH](+), which fragmented further to yield the radical molecular ion [PAH](+.). Based on significant differences in relative intensities of [Ag+2(PAH)](+), [Ag+PAH](+) and [PAH](+.), isomeric PAHs can be differentiated. The [PAH](+.)/[Ag+PAH](+) ion intensity ratio was found to increase with decreasing ionization potentials (IPs) of PAHs. The ratio was significantly different for the isomeric PAHs studied over a wide range of PAH concentrations (1.6-100 nmol/mL), and showed good measurement reproducibility; the coefficient of variation of inter-day measurements was in the range 3-12% for four representative PAHs (n = 5). Detection limits for phenanthrene, pyrene, chrysene and benzo[a]pyrene, in the form of the monomer complexes [(107)Ag+PAH](+) and measured in the selected-ion monitoring (SIM) mode, were 0.31, 0.63, 0.16 and 1.25 pmol/5 microl injection, respectively (S/N ratio approximately 2-3).     

Epigenetic modulation as a therapeutic approach for pulmonary arterial hypertension

Pulmonary arterial hypertension (PAH) is a rare but progressive and currently incurable disease, which is characterized by vascular remodeling in association with muscularization of the arterioles, medial thickening and plexiform lesion formation. Despite our advanced understanding of the pathogenesis of PAH and the recent therapeutic advances, PAH still remains a fatal disease. In addition, the susceptibility to PAH has not yet been adequately explained. Much evidence points to the involvement of epigenetic changes in the pathogenesis of a number of human diseases including cancer, peripheral hypertension and asthma. The knowledge gained from the epigenetic study of various human diseases can also be applied to PAH. Thus, the pursuit of novel therapeutic targets via understanding the epigenetic alterations involved in the pathogenesis of PAH, such as DNA methylation, histone modification and microRNA, might be an attractive therapeutic avenue for the development of a novel and more effective treatment. This review provides a general overview of the current advances in epigenetics associated with PAH, and discusses the potential for improved treatment through understanding the role of epigenetics in the development of PAH.     

Electrochemical Properties of a Boron‐Doped Diamond Electrode Modified with Gold/Polyelectrolyte Hollow Spheres

Oppositely charged polyelectrolyte (poly(allyamine hydrochloride) (PAH) and poly(sodium 4‐styrene‐sulfonate) (PSS)), and negatively charged gold nanoparticles (Au) were assembled alternately on polystyrene (PS) spheres via layer‐by‐layer technique, and the different PAH/(PSS/PAH)_n/(Au/PAH)_m/Au composite hollow spheres were derived by dissolving PS core. These hollow spheres were used to modify boron‐doped diamond (BDD) electrodes for electrochemical sensors. The cyclic voltammetric results for dopamine (DA) detection demonstrated that hollow‐sphere‐modified BDD exhibited better electrocatalytic activity than did bare BDD. Influence of the wall thickness and composition of hollow spheres on electrochemical properties were investigated. The results showed that the oxidative peak potential of DA and the peak current varied with different PSS/PAH and Au/PAH layers. The optimized wall structure of hollows spheres was PAH/(PSS/PAH)₇/(Au/PAH)₅/Au.     

Universal Calibration Method for the Determination of Polycyclic Aromatic Hydrocarbons by High Performance Liquid Chromatography with Broadband Diode-Array Detection

Abstract

The response of polycyclic aromatic hydrocarbons (PAH) at different UV wavelengths was measured using high performance liquid chromatography with spectrophotometric diode-array detection. By utilizing the total UV absorption bandwidth (200-400 nm), it was found that a narrow distribution of normalized response factors (area/g) could be obtained for 16 PAH in a reference mixture of frequently-occurring species, even though the PAH represented a wide variety of different chromophores.

Using the mean response factor for the 16 PAH, a universal calibration factor was obtained that formed the basis of a method for the determination of PAH for which calibration data cannot otherwise be obtained. It utilized normal phase high performance liquid chromatography (HPLC) with a cyanopropyl column and a hexane-dichloromethane mobile phase. The HPLC conditions were optimized for the separation of PAH according to their aromatic ring number. The method was developed for the characterization of complex mixtures of fossil fuels-derived PAH that cannot be analyzed by traditional methods. It is applicable to PAH having from 1 to 10 or more fused aromatic rings.     

The solid-matrix room-temperature luminescence detection and characterization of polyaromatic hydrocarbons without a heavy atom

A selective and sensitive method to detect polyaromatic hydrocarbons (PAH) using a new solid-matrix room-temperature luminescence technique is presented. The solid-matrix room-temperature fluorescence (SMRTF) and phosphorescence (SMRTP) of PAH can be readily obtained by adsorbing a PAH on Whatman 1PS filter paper. Strong phosphorescence can be detected without adding a heavy atom. Detection limits, ranging from 0.12 to 18 ng, were obtained for several PAH.     

The pH stimulated reversible loading and release of a cationic dye in a layer-by-layer assembled DNA/PAH film

Through the layer-by-layer (LbL) deposition method, DNA was assembled into an ultrathin film with a cationic poly(allylamine hydrochloride) (PAH). The loading and release of a typical cationic dye, 5, 10, 15, 20-tetrakis(4-N-methylpyridyl)porphine-tetra-(p-toluenesulfonate) (TMPyP), in the DNA/PAH films were investigated. It has been found that the LbL-assembled DNA/PAH film was very stable in both acidic and alkaline solutions. Stimulated by the pH change of the dye solution, the dye can be easily loaded into or released from the DNA/PAH film. In an alkaline solution, the dye could be rapidly loaded into the DNA/PAH film at room temperature, while in an acidic solution, the dye could be rapidly released. The mechanism of such pH-stimulated loading and release in the DNA/PAH film was discussed. It was further observed that the loading and release of the dye in the DNA/PAH film was reversible upon pH change and the process could be repeated many times.     

Monitoring of time variation and effect of some meteorological parameters in polynuclear aromatic hydrocarbons in Ioannina, Greece with the aid of HPLC-fluorescence analysis

This paper describes the monitoring of 16 polynuclear aromatic hydrocarbons (PAH) in the suspended particulate matter in the area of Ioannina. A total of 244 samples were collected from five locations throughout the city. These samples were analyzed in order to acquire a complete picture of the PAH abundance and distribution above the city of Ioannina. The sampling sites covered the center of the city as well as the suburban territory. The monitoring lasted for one year starting in November 1996. Higher values of PAH were found at the sites surrounding the city center, while at the rest of the area the concentration of PAH was substantially lower. The effect of ambient temperature and humidity on PAH abundance and distribution was also evaluated. As a result it was revealed that higher concentrations of PAH are favored by low temperatures and high values of humidity. Regarding the seasonal variation of PAH it was found that their concentrations are elevated during the winter months where heating systems are operating. On a daily basis it appears that the highest abundances of PAH occur on Wednesdays while the lowest on Sundays. The mean yearly concentration values of benzo[a]pyrene varied between 0.32+/-0.02 and 2.63+/-0.08 ng m(-3) for the various sites. Compared with the reported values the PAH levels in the area of Ioannina can be characterized as medium to low.     

Electrostatic cross-linking-induced self-assembly of poly(allylamine hydrochloride) using Allura Red AC

The self-assembly of poly(allylamine hydrochloride) (PAH) through electrostatic cross-linking using Allura Red AC (AR) was explored in an aqueous solution. PAH showed no self-assembly in the absence of AR. A light-scattering study demonstrated that PAH formed aggregates of ca. 300-nm diameter by the addition of AR at 0.1 of the molar ratio of the SO₃Na unit of AR to NH₃Cl of PAH (SO₃Na/NH₃Cl). The PAH diameter decreased as the SO₃Na/NH₃Cl ratio increased up to 0.5 and thereafter rapidly increased due to sedimentation of the aggregates. The analysis of the normalized time correlation function of the scattered field confirmed that the electrostatic cross-linking by AR provided polydispersed aggregates of PAH. The UV analysis revealed that the PAH self-assembly caused a blue shift of AR. The size of the aggregates was independent of the PAH concentration. On the other hand, the aggregate size was strongly dependent on the temperature.     

Simultaneous spray coating of interacting species: general rules governing the poly(styrene sulfonate)/poly(allylamine) system

Simultaneous spraying of two solutions of interacting species onto a substrate held vertically leads to the formation of nanometer-sized coatings. Here we investigate the simultaneous spraying of poly(styrene sulfonate) (PSS) and poly(allylamine hydrochloride) (PAH) solutions leading to the formation of a film composed of PSS/PAH complexes. The thickness of this film increases linearly with the cumulative spraying time. For a given spraying rate of PAH (respectively PSS), the growth rate of the film depends strongly upon the PSS/PAH ratio and passes through a maximum for a PSS/PAH ratio lying between 0.55 and 0.8. For a PSS/PAH ratio that is maintained constant, the growth speed of the film increases linearly with the spraying rate of polyelectrolyte of both solutions. Using X-ray photoelectron spectroscopy, we find that the film composition is almost independent of the PSS/PAH (spayed) ratio, with composition very close to 1:1 in PSS:PAH film. The 1:1 PSS:PAH composition is explained by the fact that the simultaneous spraying experiments are carried out with salt-free solutions; thus, electroneutrality in the film requires exact matching of the charges carried by the polyanions and the polycations. Zeta potential measurements reveal that, depending on whether the PSS/PAH spraying rate ratio lies below or above the optimal spraying rate ratio, the film acquires a positive or a negative excess charge. We also find that the overall film morphology, investigated by AFM, is independent of the spraying rate ratio and appears to be composed of nanometer-sized grains which are typically in the 100 nm range.     

Determination of selected polycyclic aromatic hydrocarbons and oxygenated polycyclic aromatic hydrocarbons in aerosol samples by high-performance liquid chromatography and liquid chromatography–tandem mass spectrometry

Fine and ultrafine particles are probably responsible for numerous health effects, but it is still unclear whether and to what extent the particle itself or organic compounds adsorbed or condensed on the particle are responsible for the effects observed. One important class of particle-bound substances are the polycyclic aromatic hydrocarbons (PAH) and their oxygenated derivatives. To improve the tools used for chemical characterization of particulate matter analytical methods for the determination of PAH and oxygenated PAH in aerosol samples of different origin have been developed and optimized. PAH on high-volume filters and on soot aerosols were analyzed by using accelerated solvent extraction for extraction and high-performance liquid chromatography with fluorescence detection for separation and quantification. Total PAH concentrations were in the range 0.3–9.3 ng m^–3. For analysis of selected oxygenated PAH on high-volume filters a liquid chromatography–tandem mass spectrometric method was developed and optimized. Preliminary investigations showed that oxygenated PAH at pg m^–3 concentrations can be determined.     

Oxidative Stress and Antioxidative Therapy in Pulmonary Arterial Hypertension

Pulmonary arterial hypertension (PAH) is clinically characterized by a progressive increase in pulmonary artery pressure, followed by right ventricular hypertrophy and subsequently right heart failure. The underlying mechanism of PAH includes endothelial dysfunction and intimal smooth muscle proliferation. Numerous studies have shown that oxidative stress is critical in the pathophysiology of PAH and involves changes in reactive oxygen species (ROS), reactive nitrogen (RNS), and nitric oxide (NO) signaling pathways. Disrupted ROS and NO signaling pathways cause the proliferation of pulmonary arterial endothelial cells (PAECs) and pulmonary vascular smooth muscle cells (PASMCs), resulting in DNA damage, metabolic abnormalities, and vascular remodeling. Antioxidant treatment has become a main area of research for the treatment of PAH. This review mainly introduces oxidative stress in the pathogenesis of PAH and antioxidative therapies and explains why targeting oxidative stress is a valid strategy for PAH treatment.     

Capillary GC analysis of diesel fuels using simultaneous parallel triple detection

Diesel fuels from different parts of the UK have been analyzed for polycyclic aromatic hydrocarbons (PAH), nitrogen-containing PAH, and sulfur-containing PAH using capillary column GC with simultaneous parallel triple detection. The concentrations of polyaromatic compounds (PAC) were high and showed considerable variability amongst the fuels. The PAH are mainly naphthalene, fluorene, and phenanthrene and their alkylated homologs; the PANH are mainly carbazole and its methyl derivatives; the PASH are mainly dibenzothiophene and its methyl derivatives.     

Pilot study: PAH fingerprints of aircraft exhaust in comparison with diesel engine exhaust

In the course of a preliminary investigation the PAH fingerprints from diesel engines were compared with those from aircraft turbines. The goal was to determine whether PAH fingerprints permit to distinguish between the sources of air and road traffic. The results showed that the PAH spectra of both sources do not vary significantly. However, in turbine exhaust gas p-quaterphenyl was found, that is untypical for diesel engines. So this component may be a tracer for PAH pollution from aeroplanes.     

焦炉烟气中全量多环芳烃分析方法

报道了利用处在制串联采样装置。优选出了比较理想的前处理方法，并用此方法对焦炉烟气中的全量多环芳烃进行了研究。滤膜颗粒物中的多环芳烃有６途中 ，聚氨酯泡沫吸附剂中有４９种。     

Polycyclic aromatic hydrocarbons in Ya-Er Lake (Hubei, China): sources and distribution

Sources and distribution of polycyclic aromatic hydrocarbons (PAH) in the Ya-Er Lake area (Hubei, China) sediment cores of 3 ponds in the shallow Ya-Er Lake were investigated for 16 PAH. Analytical procedure included extraction by ultrasonication, clean-up by gel-permeation and quantification by HPLC with fluorescence detection. The total PAH amount in sediment samples of the Ya-Er Lake ranged from 68 to 2242 μg/kg. Concentrations decreased from pond 1 to pond 3 and from upper to lower sediment layers. In addition a soil sample from Ya-Er Lake area showed a total PAH amount of 58 μg/kg. The PAH pattern in lower sediment layers were similar to that of the soil sample which indicates an atmospheric deposition into the sediments prior to 1970 only. The PAH profile of upper sediment samples, which differs completely from that of lower layers, may be explained by a gradually increasing input of mixed combustion and raw fuel sources since 1970. Therefore the origin of increased PAH contamination in Ya-Er Lake during the last 3 decades has been probably an industrial waste effluent in pond 1.     

Direct LD-FTMS detection of mineral-associated PAHs and their influence on the detection of co-existing amino acids

Polycyclic aromatic hydrocarbon (PAH) compounds and amino acids (AAs) are both ubiquitous throughout the universe and can be co-located in mineral matrices (e.g., meteorites); therefore, co-detection of PAHs and AAs associated with terrestrial and extra-terrestrial minerals is of interest. Nine PAH compounds representing four chemical classes of PAH (unsubstituted, acetyl-, amino-, and nitro-substituted) were applied onto the surface of quartz, plagioclase, olivine, and ilmenite mineral standards and analyzed using laser desorption/ionization Fourier transform mass spectrometry (LD-FTMS). Mass-to-charge peaks derived from PAH compounds were detected from the surfaces of all minerals evaluated. All PAH compounds were detected in the positive ion mode, whereas only nitro-substituted PAH compounds were detected in negative ion mode. In this and earlier studies, the ability to directly detect mineral-associated AAs by LD-FTMS was dependent on the mineral geomatrix. On iron-bearing minerals AAs appeared as highly fragmented ions in the spectra or were not detectable; however, the addition of the PAH chrysene enabled the ionization and detection of AAs threonine and histidine by LD-FTMS. Thus, for mineral systems such as meteorites, interstellar dust particles, soils, and sediments, the co-detection of AAs associated with PAHs by LD-FTMS is feasible.     

Comparison of stir bar sorptive extraction (SBSE) and liquid-liquid extraction (LLE) for the analysis of polycyclic aromatic hydrocarbons (PAH) in complex aqueous matrices

Stir bar sorptive extraction (SBSE) is an equilibrium extraction method used amongst others for the analysis of polycyclic aromatic hydrocarbons (PAH) in aqueous samples. We compared SBSE to liquid-liquid extraction (LLE) for aqueous eluates obtained from batch and column tests of PAH contaminated soils to check whether SBSE might be considered as an alternative sample preparation method. We used soils with different particle size distribution, organic matter content, and resulting eluate turbidity to test the sample preparation methods on eluates with matrices of varying complexity. Furthermore, we studied the influence of diluted organic matter (DOM) on the PAH sorption process to the polymer coating of the stir bar during SBSE. In the majority of cases, we found higher PAH concentrations (up to 288%) with SBSE than with LLE. The turbidity correlates with the difference in PAH results, i.e. the greater the turbidity in the eluate, the more PAH we found with SBSE compared to LLE. We observed no similar trend regarding the amount of total organic carbon (TOC). The presence of DOM in the eluate seems to hamper the SBSE slightly, the PAH recovery varied between 82 and 104%.     

Determination of 23 polycyclic aromatic hydrocarbons in atmospheric particulate matter of the Paris area and photolysis by sunlight

Twenty-three polycyclic aromatic hydrocarbons (PAH) were determined in atmospheric particulate matter in 4 places of the Paris area at several times of the year. Fractionation was performed by reversed-phase high-pressure liquid chromatography. Determination was done by recording emission or excitation fluorescence spectra via a stopped-flow technique. Triphenylene was also extemporaneously determined by its phosphorescence spectrum at low temperature. Among the PAH determined dibenz(e,ghi)perylene has not been detected before in atmospheric particulate matter. The 10 more abundant PAH ranged from 0.1 to 40 ng/m3 of filtered air. Concentrations in August are from 14 to 250 times less than in January depending on the PAH. The reasons for this difference of behaviour among the PAH were investigated with regard to their photochemical and non-photochemical reactivity.