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Naphthalene diimides with one and two metal-chelating Gly-Gly-His (GGH) motifs have been synthesized. Both conjugates induce single-stranded cleavage of plasmid pBR322 DNA in the presence of nickel and Oxone and are approximately 100-fold more efficient than Ni(II) x GH-CONH2 itself.
Naphthalene diimides function as effective intercalators and when tethered to the 5'-terminus of a pyrimidine-rich oligonucleotide can contribute significantly to the overall stabilization of DNA triplexes. This stabilization can be further enhanced by alterations to the linker tethering the DNA sequence and the intercalator. Less flexible linkers, and particularly one with a phenyl ring present, appear to permit the stabilization afforded by the bound intercalator to be transferred more effectively to the three-stranded complex. The conjugate containing the phenyl linker exhibits a T(M) value that is increased by 28 degrees C relative to the unconjugated triplex. That the linker itself contributes to the observed stabilization is clear since introduction of the phenyl linker increases the observed T(M) by 11 degrees C relative to a simple flexible linker.
A combinatorial mini library of naphthalene substituted chalcones has been prepared by solution phase chemistry. Screening of these mixtures for leukotriene B4 inhibitory activity using human whole blood assay (HWBL) afforded a lead compound, 1-(6-butoxy-2-naphthyl)-3-(4-nitrophenyl)-prop-2-en-1-one (K4A3) with an IC50 value of 18.5 microM.
Using the water-soluble naphthalene carrier of singlet oxygen NDPO2, we have shown that pure singlet oxygen is able to inactivate enveloped viruses (human immunodeficiency virus type 1, herpes simplex virus type 1, cytomegalovirus, vesicular stomatitis virus), but has no effect on non-enveloped viruses (adenovirus and poliovirus 1). These results are related to the experiments on photoinactivation of viruses by hydrophobic photosensitizers (merocyanine 540, hypericin, phthalocyanines, hematoporphyrin and benzoporphyrin derivatives) and they strengthen the hypothesis that singlet oxygen plays a predominant role in this process.
An ion-pair solid-phase extraction (IPE), ion-pair chromatography (IPC) procedure with fluorescence detection for the quantitative analysis of sulfonated naphthalene-formaldehyde condensates (SNFC) was developed, which provides full resolution of SNFC up to a degree of condensation n = 5 and partial resolution up to n = 15. Liquid chromatography-electrospray ionization-mass spectrometry confirmed that SNFC elute in the order of condensation. Response factors in fluorescence detection proved to be mass-constant, thereby allowing us to determine total SNFC amounts. With this IPC method, the weight- and the number-average molecular weights of these high-volume production chemicals (kiloton per annum), used as synthetic tanning agents, concrete plasticizers, and dispersants, can be determined. Recoveries in IPE range from 73 to 85% in river Rhine water and from 79 to 93% in tap water for n = 2 to n = 7 with limits of detection of 3-8 ng/L for individual homologues from 500 mL of water. The IPE-IPC procedure was applied to samples of secondary industrial effluents, river Rhine water, a river bank filtrate, and a groundwater sample. SNFC up to n = 6 were detected in the treated effluents. Total concentrations ranged from 208 micrograms/L in a secondary treated SNFC production effluent to < 1.4 micrograms/L in groundwater. These first analyses suggest a widespread occurrence of the lower oligomers of SNFC in the aquatic environment.
Naphthalene-2,3-dicarboxaldehyde (NDA) has been investigated as a new derivatizing reagent for the electrochemical detection of tagged amino acids. Gradient elution allowed for the separation of 18 NDA-derivatized amino acids on an open tubular liquid chromatography column in less than 50 min. Gradient elution and electrochemical detection were found to be compatible. A detection limit of 36 amol was obtained for the asparagine-NDA derivative. The usefulness of this technique for quantitation was demonstrated by the analysis of the NDA-tagged hydrolysis products from bovine chymotrypsinogen.
The ionization mechanism in dopant-assisted atmospheric pressure photoionization and the effect of solvent on the ionization efficiency was studied using 7 naphthalenes and 13 different solvent systems. The ionization efficiency was 1-2 orders of magnitude higher with dopant than without, indicating that the photoionization of the dopant initiates the ionization process. In positive ion mode, the analytes were ionized either by charge exchange or by proton transfer. Charge exchange was favored for low proton affinity solvents (water, hexane, chloroform), whereas the addition of methanol or acetonitrile to the solvent initiated proton transfer. In negative ion mode, the compounds with high electron affinity were ionized by electron capture or by charge exchange and the compounds with high gas-phase acidity were ionized by proton transfer. In addition, some oxidation reactions were observed. All the reactions leading to ionization of analytes in negative ion mode are initiated by thermal electrons formed in photoionization of toluene. The testing of different solvents showed that addition of buffers such as ammonium acetate, ammonium hydroxide, or acetic acid may suppress ionization in APPI. The reactions are discussed in detail in light of thermodynamic data.
Peptide nucleic acids (PNAs) are neutral DNA analogues, which bind single-stranded DNA (ssDNA) strongly and with high sequence specificity. However, binding efficiency is dependent on the purine content of the PNA strand. This property make more difficult application of PNA as hybridization probes in, e.g., PNA chips, since at a set temperature the hybridization of a fraction of the DNA targets to the PNA probes does not obey Watson-Crick binding rules. The polypurine PNAs, for example, bind the mismatch containing DNA targets stronger, than the pyrimidine rich PNAs their fully complementary targets. Herein we show that PNA-DNA binding efficiency can be finely tuned by the conjugation of derivatives of naphthalene diimide (NADI) to the N-terminus of PNA using polyamide linkers of different lengths. This approach can potentially be used for the design of PNA probes, which bind their DNA targets with similar affinity independently of the PNA sequence.
Naphthalene diimide (NDI), a powerful oxidant that binds avidly to DNA by intercalation, is seen to damage the 5' guanine of 5'-GG-3' sites by photoactivated charge transport through DNA. When covalently tethered to the center of a triplex-forming oligonucleotide and delivered by triplex formation within a pyrimidine.purine-pyrimidine motif to a specific site on a restriction fragment, NDI can photooxidize guanine over at least 25-38 bp in each direction from the site of binding. Charge migration occurs in both directions from the NDI intercalator and on both DNA strands of the target, but the oxidation is significantly more efficient to the 3' side of the triplex. NDI and octahedral rhodium intercalators, when tethered directly to the 5' terminus of the triplex-forming strand as opposed to the center, generate significant amounts of oxidative damage only in the immediate vicinity of the intercalation site. Given that long-range charge transport depends on DNA stacking, these results suggest that the base stack is distorted at the 5' end of the triplex region in the duplex-triplex junction. Targeting of photooxidative damage by triplex formation extends our previous studies of long-range charge transport to significantly longer DNA sequences through a strategy that does not require covalent attachment of the photooxidant to the DNA being probed. Moreover, triplex targeting of oxidative damage provides for the first time a typical distance distribution for genomic charge transport of approximately 200 A around the oxidant.
Environmentally sensitive fluorescent probes involve two groups, an electron donor and an electron acceptor, attached to an aromatic ring system, and maximal effects may be expected when these groups are as far apart as feasible. The syntheisis, characterization, and spectroscopic properties of 6-propionyl-2-(dimethylamino)naphthalene (PRODAN), a compound that fulfills these conditions, are described. The maximum of emission is at 401 nm in cyclohexane solution and at 531 nm in water solution, indicating an increase of dipole moment of approximately 20 D units on excitation to the lowest singlet state. The effect of temperature upon the spectral distribution and the bandwidth of fluorescence of PRODAN in 1:1 complexes with albumin shows the existence of a dynamic relaxation process of the protein surroundings within th 2-4 ns of the fluorescence lifetime.
It is the first time that the removal of polycyclic aromatic hydrocarbons (PAH) containing different aromatic rings number [naphthalene (Np), phenanthrene (Phe), and pyrene (Py)] from combustion hot gas has been carried out. The aim was to relate the sorbents textural characteristics with the adsorption capacity of these 2-4-ring PAH at the conditions emitted at energy generation. The sorbents textural parameters [total micropore volume (VN2), narrow micropore volume (VCO2), mesopore volume (VBJH), and the free active sites] were analyzed trying to correlate them with their Np, Phe, and Py adsorption capacities. To get this aim, single and multiple linear regressions (MLR) were applied to the three PAH. A principal component analysis was performed to generate new and uncorrelated variables. It enabled us to show that the relations between the textural parameters were analyzed using a principal components regression (PCR). The PCR analysis had a good statistical quality, but neither did it allow differentiating free active site types nor did VN2 and VCO2. The correlations were thus set up applying a MLR to the original variables. The regression statistical quality was similar to the PCR analysis, and it could give an easier explanation of the parameters that affected the adsorption. In Np adsorption, the 87% data variance was explained, and the adsorption was positively correlated to VCO2 and the micropore mean diameter (I.). In the Phe regression there was 98% variance explained, and its adsorption was positively correlated to the VN2 and the micropore distribution, n. Finally, in the Py adsorption, the 96% data variance was explained, and this adsorption was positively correlated to VN2 and VBJH. These dependencies were according to the molecular parameters of these compounds (molecular diameter and volatility) because the higher the number of aromatic rings of the PAH, the more favored the adsorbate-adsorbate interactions. Besides, the higher the mean diameter micropores, the lower the diffusional problems showed by Np, Phe, and Py.
Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs), naphthalenes (PCNs), and biphenyls (PCBs) were measured in eggs of double-crested cormorants and herring gulls collected from Michigan waters of the Great Lakes. Concentrations of PCNs in eggs of double-crested cormorants and herring gulls were in the ranges of 380-2400 and 83-1300 pg/g, wet wt, respectively. Concentrations of 2,3,7,8-substituted PCDDs and PCDFs were 10-200 times less than those of PCNs in eggs whereas those of total PCBs (380-7900 ng/g, wet wt) were 3-4 orders of magnitude greater. While the profile of PCB isomers and congeners between double-crested cormorants and herring gulls was similar, the PCN isomer profile differed markedly between these two species. PCN congeners 66/67 (1,2,3,4,6,7/1,2,3,5,6,7) accounted for greater than 90% of the total PCN concentrations in herring gulls, whereas their contribution to total PCN concentrations in double-crested cormorants ranged from 18 to 40% (mean, 31%). The ratios of concentrations of PCDDs to PCDFs were greater in herring gulls than in double-crested cormorants collected from the same locations, suggesting the ability of the former to metabolize PCDF congeners relatively rapidly. 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) equivalents (TEQs) contributed by PCNs in double-crested cormorant and herring gull eggs were 2-3% of the sum TEQs of PCBs, PCDDs, PCDFs, and PCNs. PCB congener 126 (3,3',4,4',5-PeCB) accounted for 57-72% of the total TEQs in double-crested cormorant and herring gull eggs.
Polychlorinated naphthalenes (PCNs) have been analyzed in archived soil from the U.K. to investigate historical trends. Samples were obtained from the Broadbalk experiment plots (1944-1986) and Luddington experiment station (1968-1990). Luddington samples also include a set of soils that received a one-time sludge treatment in 1968, and duplicate samples of this archived sludge were also analyzed. Peak residues of sumPCN (sum of all PCN congeners quantified) were approximately 9000 pg g(-1) dry weight in 1956, declining to approximately 300 pg g(-1) in contemporary soils. The one-time sludge application resulted in elevated soil residues that were 1.5-6 times higher than the control plot over the time series. This increase is consistent with the known application rate and the amount of sumPCN in the applied sludge (approximately 250,000 pg g(-1) dry wt). Half-lives forthe Luddington control soil and the sludge-amended soil for the period 1972-1990 were 5.3 and 9.9 years, respectively. Investigation of time trends revealed differences between homologue groups with the higher molecular weight congeners peaking earlier in the time series (pre-1950) and the lower molecular weight congeners peaking later, ca. 1970. Time trends of individual congeners were investigated in terms of their relative mass percent contribution to the sum of their homologue group. Significant (p < 0.05) increasing trends were observed for several congeners associated with combustion sources (CN-29, -51, -52/60, -54, and -66/67) suggesting that combustion related sources are more important now than they were in the past. However, no decreasing trend was observed for congeners that were thought to be susceptible to degradation by photolysis suggesting that this may not be a key elimination pathway of PCNs in the environment. A simple calculation of the fugacity status of PCNs in air and soil showed that the tri-CNs are exhibiting net outgassing, while the penta-CNs are still being deposited to soil. Interestingly, the penta-CNs associated with combustion show the largest gradient for air-to-soil transfer, supporting the notion that combustion sources are important contributors to contemporary air burdens of these congeners.
The scientific literature contains little information regarding bioaccumulation and biomagnification of polychlorinated naphthalenes (PCNs) in food webs. Here we present new information on the food chain transfer of PCNs within a food chain in a subarctic environment PCNs (tetra- to hepta-chloro congeners) were measured in surface sediments and in a marine benthic food chain, comprising amphipods, isopods, and fourhorned sculpins. Samples were collected from five locations in the Gulf of Bothnia, northern Baltic Sea. PCN concentrations in the sediments were similar to background levels determined previously in sediments from the northern hemisphere. Measurement of the carbon content of the sediments allowed the calculation of biota to sediment accumulation factors (BSAFs). Tetra- and penta-CNs exhibited BSAF values greater than one, while BSAFs for the more chlorinated PCNs were less than one. This suggests more efficient assimilation, by amphipods, of the less chlorinated PCNs. A decrease in sigmaPCN concentrations from the lowest to the highest trophic level was demonstrated (amphipods: 10-69 ng/g lw, isopods: 3.9-16 ng/g lw; fourhorned sculpins: 0.54-1.5 ng/g lw). Biomagnification factors (BMFs) were calculated based on the concentrations of the congeners. These indicated that a few congeners biomagnified significantly: the highest BMFs (0.09-1.4) were found for 2,3,6,7-substituted congeners and those lacking adjacent hydrogen-substituted carbon atoms.
Polychlorinated naphthalenes (PCNs) and mono- and non-ortho substituted PCBs were analyzed in air from two sites in Toronto, Ontario, Canada to determine whether current combustion-related sources contribute to the levels and profiles of PCNs found in urban air. High-volume air samples were collected periodically at the University of Toronto (UT, a downtown site) and in north Toronto at the Meteorological Service of Canada (MSC). SigmaPCN concentrations ranged from 31 to 78 pg m(-3) at UT and from 7 to 84 pg m(-3) at MSC with concentrations lower at MSC than UT for paired samples. Ambient air congener profiles contrasted between the two sites with MSC profiles indicating inputs from combustion-related sources when compared to combustion fly ash and technical PCN and PCB mixture profiles. Combustion markers, including CN-44, -29, and -54, the more toxic CN-66 and -67 congeners, and non-ortho PCBs, were enriched in air at MSC on a mass percent basis in several samples. As a result, CN-66/67 contributed proportionally more to dioxin toxic equivalents at MSC than at UT. Downtown air PCN profiles resembled those of technical PCN and PCB mixtures, reflecting evaporative emissions from past uses, while PCN levels and profiles at MSC, a more industrialized location, are also influenced by current combustion sources, contributing as much as an estimated 54% of sigmaPCN in samples collected.
Concentrations of polychlorinated naphthalenes (PCNs) were measured in foodstuffs randomly acquired in seven cities of Catalonia, Spain. A total of 108 samples, belonging to 11 food groups (vegetables, tubers, fruits, cereals, pulses, fish and shellfish, meat and meat products, eggs, milk, dairy products, and oils and fats), were analyzed by high-resolution gas chromatography/high-resolution mass spectrometry (HRGC/HRMS). The levels of tetra-, penta-, hexa-, and hepta-CNs, those of octachloronaphthalene, and the mean sum concentration of tetra-octa-CN were determined. The highest concentration of total PCNs was found in oils and fats (447 pg/g), followed by cereals (71 pg/g), fish and shellfish (39 pg/g), and dairy products (36 pg/g). In general, tetra-CN was the predominant homologue in all food groups except for fruits and pulses, which had greater proportions of hexa-CNs. The dietary intake of total PCNs was subsequently determined. For calculations, recent data on consumption of the selected food items were used. Intake of PCNs was estimated for five population groups of Catalonia: children, adolescents, male and female adults, and seniors. When the dietary intake of total PCNs was expressed in nanogram per kilogram of body weight per day, it was age-dependent, with the highest and lowest values corresponding to children (1.65) and seniors (0.54), respectively. The largest contribution to the daily PCNs intake came from oils and fats and from cereals. The result of the current study is the first published report concerning human exposure to PCNs through the diet.
Polychlorinated naphthalenes (PCNs) with four to eight chlorines were studied in air collected at two background stations in Sweden, one southerly and one northerly. Air was sampled with a high-volume sampler, and gas-phase adsorbents and filters were analyzed separately. The sum of TeCNs to HxCNs in the gaseous phase ranged between 1 and 10 pg/m3 with significantly higher concentrations at the southern location Hoburgen. HpCNs and OCN were below the detection limit. The highest concentrations were found in two samples from Hoburgen with the air masses coming from SW and W and during warm weather (+11 degrees C). The lowest concentration was found in a sample from the northern location Ammarnäs at cold weather (-22 degrees C) when the air came from the east. A correlation was found between logP and 1/T indicating that temperature has a larger effect than location on the concentration in the gas phase. The TeCNs constituted 50-75% in the gaseous phase. In most filter samples TeCNs and PeCNs were below the limit of quantitation. PUF samples with air trajectories from W to NE had relatively higher concentrations of late eluting TeCNs and PeCNs, while in samples with winds from SE to S the early eluting congeners dominated. Samples with early eluting congeners were mainly collected at lower temperature. TriCNs constituted the dominant homologue group both in the gaseous and particulate phase of air samples as well as in bulk deposition from a rural monitoring station south of Stockholm. The octanol-air partition coefficient described the gas/particle interaction well for samples collected at temperatures down to -8 degrees C.
To improve understanding of air-to-vegetation transfer of persistent organic pollutants (POPs), uptake and depuration of polychlorinated biphenyls (PCBs) and polychlorinated naphthalenes (PCNs) between grass sward and air was investigated. Pasture swards were placed in fanned (2 m s(-1) wind speed) and unfanned conditions for a period of 20 days and sampled at intervals. Depuration was carried out after a short (4 days) and a long (14 days) exposure period. Prior to contamination, a mixed pasture sward at a semi-rural location contained sigmaPCN concentrations 15-20% of the sigmaPCB concentration. Uptake of both PCBs and PCNs was broadly linear in fanned and unfanned conditions over the 20-day period, i.e., the pasture did not reach equilibrium with the air. Uptake rates (fluxes) were greater under the fanned conditions. The difference in uptake rates between fanned and unfanned conditions increased with degree of chlorination for both PCBs and PCNs, ranging between a factor of 2 for tri-chlorinated PCBs and PCNs and a factor 5 for octa-chlorinated PCBs. Depuration results over the first hours were very scattered, showing an initial period of loss, followed by an increase in concentrations, possibly as a result of re-volatilization of PCBs from the soil in the trays, with consequent recapture by the overlying sward. Rapid clearance was observed over the following days, but depuration of PCBs and PCNs was still incomplete after 14 days, with 20% of the initial concentration of the sigmaPCBs and 10% of the sigmaPCNs retained by the sward. There was no difference in the proportion of POPs retained in the sward between the 4- and 14-day contamination treatments. POP-specific differences in the amount of compound "trapped" in leaves after contamination were observed. The results show that, although changes in the rate of air movement around a pasture have an effect on the uptake rate of POPs into the vegetation, plant-side resistance controls both the air-to-pasture and pasture-to-air exchange of gas-phase PCBs and PCNs; i.e., differences between plant species in cuticle composition and/or structure affecting the permeability of the cuticle are of greater importance than differences in leaf morphology affecting aerodynamic roughness.