Surface sediments collected from nine urban rivers located in Zhongshan City, Pearl River Delta, were analyzed for total concentration of metals with digestion and chemical fractionation adopting the modified European Community Bureau of Reference (BCR) sequential extraction procedure. The results showed that concentration and fractionation of metals varied significantly among the rivers. The total concentration of eight metals in most rivers did not exceed the China Environmental Quality Standard for Soil, Grade III. The potential ecological risk of metals to rivers were related to the land use patterns, in the order of manufacturing areas > residential areas > agriculture areas. The concentration of Pb in the reducible fraction was relatively high (60.0-84.3%). The dominant proportions of Cd, Zn and Cu were primary in the non-residual fraction (67.0%, 71.8% and 81.4% on average respectively), while the percentages of the residual fractions of Cr and Ni varied over a wide range (43-85% and 24-71% respectively). The approaches of the Håkanson ecological risk index and Secondary Phase Enrichment Factor were applied for ecological risk assessment and metal enrichment calculation. The results indicated Hg and Cd had posed high potential ecological risk to urban rivers in this region. Meanwhile, there was widespread pollution and high enrichment of Cu in river sediments in this region. Multiple regression analysis showed that five water quality parameters (pH, DO, COD(Mn), NH(4)(+)-N, TP) had little influence on the distribution of metal fractionation. This result revealed that the ecological risk of metals was not eliminated along with the improvement in water quality. Correlation studies showed that among the metals, Group A (Cd, As, Pb, Zn Hg, r = 0.730-0.924) and Group B (Cr, Cu, Ni, r = 0.815-0.948) were obtained, and the metal contaminations were from industrial activities rather than residential.
A potential real-time imaging water-soluble fluorescent polymer (P3) is facilely prepared via one-pot method. For P3, tetraphenylethene unit serves as the fluorescent unit, poly(acryloyl ethylene diamine) (a kind of polyelectrolyte) with specific degree of polymerization acts as water-soluble part. H-NMR, gel permeation chromatography (GPC), UV-vis spectroscopy, photoluminescence (PL), and confocal laser scanning microscopy are undertaken to characterize the structure and property of P3. The results of wash-free cellular imaging show that the signal-to-noise ratio is high as the concentration of P3 is 50 μg mL . In addition, the pH-responsive and Cd -responsive are also investigated in this paper. The results coming from pH-responsive show that P3 solution displays significant fluorescence under near neutral. And the result from the cellular imaging shows that intracellular fluorescence intensity enhances with the augment of concentration of Cd , which reveals that P3 can give a hint to resolve the dilemma of traditional fluorescent dyes used as living cellular fluorescent probe.
A new water-soluble pyrene-containing fluorescent polymer, 1-{3 1-S-[poly(acryloyl ethylene diamine hydrochloride)-2 1-methyl propionic acid]}propionyloxy hexyloxy pyrene (P3) with defined structure, was designed and synthesized using the click reaction between thiol and a carbon-carbon double bond. The intermediate products P1 (S-1-dodecyl-S 1-[poly(N-Boc-acryloyl ethylene diamine)-2 1-methyl propionic acid]trithiocarbonate) and AHP (1-(acryloyloxy hexyloxy)pyrene) were prepared via reversible addition fragmentation chain transfer (RAFT) polymerization and Williamson synthesis, respectively. Conjugating AHP with P1, P2 (1-{3 1-S-[poly(N-butoxycarbonyl-acryloyl ethylene diamine)-2"-methyl propionic acid]} propionyloxy hexyloxy pyrene) was synthesized, adopting both the reduction reaction of a trithioester bond of P1 to thiol and the click reaction between thiol and the carbon-carbon double bond of AHP simultaneously. P3 was obtained by the deprotection of the resulting Boc-protected polymer (P2) with aqueous HCl. The experiment results showed that P2 exhibited a bright blue-violet emission band at approximately 387-429 nm. After deprotection, P3 displayed good solubility in water and not only exhibited a blue-violet fluorescence emission band at approximately 387-429 nm in aqueous solution but also had the similar photoluminescent spectra to those of AHP and P2 in dichloromethane. The fluorescence quantum yields of P2 in dilute tetrahydrofuran and P3 in a dilute aqueous solution were 0.44 and 0.39, respectively. This experiment provided a novel insight into the study of water-soluble fluorescent polymers.
Perylene bisimides dye-based water-soluble fluorescent polymer P3, N,N'-bis(3-amyl)-1-bromo-7-{4'-[3''-(S-poly(N-acryloyl ethylene diamine hydrochloride)-2'''-methyl propionic acid)propionyloxy hexyloxy]phenyl} perylene-3,4:9,10-tetracarboxylic bisimides, was synthesized with polyelectrolyte modification via one-pot reaction (the reduction reaction of trithioester and click reaction between the thiol group and carbon-carbon double bond were simultaneously conducted in one pot with high conversion). One-pot method can overcome the limitation that usual click reaction between thiol and other groups has low conversion because thiol group is subject to rapid oxidation during purification and storage. Chemical, structural, and optical properties of P3 and intermediate products were fully characterized by nuclear magnetic resonance spectroscopy, Fourier transform infrared, gel permeation chromatograph, UV-vis spectra, and fluorescence spectra, respectively. The results revealed that P3 displayed excellent water solubility and not only exhibited red strong fluorescence emission band in water but also had the similar photoluminescent spectra to those of intermediate products (M4 and P2) in chloroform. Allowing for the potential application in biological detection field, cell viability and live cell imaging with the presence of P3 were further investigated with Hela cells. The results showed that P3 had low cytotoxicity with strong intracellular fluorescence entry. Meanwhile, with the augment of concentration of P3 (0-0.500 mg mL(-1)), the cell uptake and accumulation of P3 increased and thereby result in enhancement of the intracellular fluorescence. These experiment results suggested that P3 had enormous potential as a fluorescence probe to be an important component in biological detection field.
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