Pollution Characteristics and Health Risk Assessment of Phthalate Esters in PSW Recycling Sites: A Typical Case Study.

The concentrations of six priority phthalate esters (PAEs) in 700 soil samples and 110 sediment samples from an area in China containing plastic solid waste (PSW) recycling sites were determined. The total concentrations of the six PAEs in soil and sediment were not detected - 274 and not detected - 597 mg kg-1, respectively, and the mean concentrations in soil and sediment were 14.4 and 31.7 mg kg-1, respectively. The dominant PAEs were di(2-ethylhexyl) phthalate and di-n-butyl phthalate. PAEs were detected in soil collected from the surface to 0.5 m below ground level around the PSW recycling sites, and the concentrations were markedly higher in these areas than at other polluted sites. PSW recycling is an important source of PAEs to soil and sediment. The di(2-ethylhexyl)phthalate concentrations in soil were higher than the relevant concentrations that pose environmental risks for sensitive land uses and non-sensitive land uses (42 and 121 mg kg-1, respectively), indicating emissions of PAEs from PSW recycling sites may pose environmental risks. The results indicate that PAE pollution at PSW sites needs to be better controlled and managed.

Metathesis Cyclopolymerization Triggered Self-Assembly of Azobenzene-Containing Nanostructure.

Azobenzene (AB) units were successfully introduced into poly(1,6-heptadiyne)s in order to ensure smooth synthesis of double- and single-stranded poly(1,6-heptadiyne)s (P1 and P2) and simultaneously realize the self-assembly by Grubbs-III catalyst-mediated metathesis cyclopolymerization (CP) of AB-functionalized bis(1,6-heptadiyne) and 1,6-heptadiyne monomers (M1 and M2). Monomers and polymers were characterized by 1H NMR, mass spectroscopy, and GPC techniques. The double-stranded poly(1,6-heptadiyne)s exhibited a large scale of ordered ladder nanostructure. This result was attributed to the π-π attractions between end groups along the longitudinal axis of the polymers and van der Waals interactions between the neighboring polymeric backbones. While the Azo chromophore connected in the side chain of P2 induced conformation of micelles nanostructure during the CP process without any post-treatment. Furthermore, the photoisomerization of Azo units had an obviously different regulatory effect on the conjugated degree of the polymer backbone, especially for the single-stranded P2, which was attributed to the structural differences and the interaction between AB chromophores in the polymers.

Design, Synthesis and Characterization of a Novel Type of Thermo-Responsible Phospholipid Microcapsule-Alginate Composite Hydrogel for Drug Delivery.

Liposomes are extensively used in drug delivery, while alginates are widely used in tissue engineering. However, liposomes are usually thermally unstable and drug-leaking when in liquids, while the drug carriers made of alginates show low loading capacities when used for drug delivery. Herein, we developed a type of thermo-responsible liposome-alginate composite hydrogel (TSPMAH) by grafting thermo-responsive liposomes onto alginates by using Ca2+ mediated bonding between the phosphatidic serine (PS) in the liposome membrane and the alginate. The temperature-sensitivity of the liposomes was actualized by using phospholipids comprising dipalmitoylphosphatidylcholine (DPPC) and PS and the liposomes were prepared by a thin-film dispersion method. The TSPMAH was then successfully prepared by bridge-linking the microcapsules onto the alginate hydrogel via PS-Ca2+-Carboxyl-alginate interaction. Characterizations of the TSPMAH were carried out using scanning electron microscopy, transform infrared spectroscopy, and laser scanning confocal microscopy, respectively. Their rheological property was also characterized by using a rheometer. Cytotoxicity evaluations of the TSPMAH showed that the composite hydrogel was biocompatible, safe, and non-toxic. Further, loading and thermos-inducible release of model drugs encapsulated by the TSPMAH as a drug carrier system was also studied by making protamine-siRNA complex-carrying TSPMAH drug carriers. Our results indicated that the TSPMAH described herein has great potentials to be further developed into an intelligent drug delivery system.

Functional Block Copolymers Carrying One Double-Stranded Ladderphane and One Single-Stranded Block in a Facile Metathesis Cyclopolymerization Procedure.

In order to improve the poor film-forming ability of polymeric ladderphane, di-block copolymers containing perylene diimide (PDI)-linked double-stranded poly(1,6-heptadiyne) ladderphane and branched alkyl side chains modified single-stranded poly(1,6-heptadiyne) were synthesized by metathesis cyclopolymerization (MCP) using Grubbs third-generation catalyst (Ru-III) in tetrahydrofuran solvent. The first block containing the ladderphane structure leads to higher thermal-stability, wider UV-vis absorption, lower LUMO level and ladderphane-induced rigidity and poor film-forming ability. The second block containing long alkyl chains is crucial for the guarantee of excellent film-forming ability. By comparing the effect of ladderphane structure on the resulted copolymers, single-stranded poly(1,6-heptadiyne) derivatives with PDI pedant were also processed. The structures of copolymers were proved by 1H NMR and gel permeation chromatography, electrochemical, photophysical, and thermal-stability performance were achieved by cyclic voltammetry (CV), UV-visible spectroscopy and thermogravimetric analysis (TGA) measurements. According to the experiment results, both copolymers possessed outstanding film-forming ability, which cannot be realized by small PDI molecules and oligomers. And they can serve as a superior candidate as for n-type materials, especially for their relatively wide range of light absorption (λ = 200~800 nm), and lower LUMO level (-4.3 and -4.0 eV).

Novel Photoresponsive Linear, Graft, and Comb-Like Copolymers with Azobenzene Chromophores in the Main-Chain and/or Side-Chain: Facile One-Pot Synthesis and Photoresponse Properties.

Novel photoresponsive linear, graft, and comb-like copolymers with azobenzene chromophores in the main-chain and/or side-chain are prepared via a sequential ring-opening metathesis polymerization (ROMP) and head-to-tail acyclic diene metathesis (ADMET) polymerization in a one-pot procedure using Grubbs ruthenium-based catalysts. The diluted solutions of these as-prepared copolymers containing azobenzene chromophores exhibit photochemical trans-cis isomerization under the irradiation of UV light, followed by their cis-trans back-isomerization in visible light. The rates of photoisomerization are found to be slower than those of back-isomerization, and the rate for the comb-like copolymer is found to be from 3 to 7 times slower than that obtained for the linear or graft copolymer. This is ascribed to the differences in structure of the copolymers and the specific location of azobenzene chromophores in the copolymer, which favor a side-chain graft structure.

Wide bandwidth and high coupling efficiency Si3N4-on-SOI dual-level grating coupler.

We propose and experimentally demonstrate fiber-to-chip grating couplers with aligned silicon nitride (Si(3)N(4)) and silicon (Si) grating teeth for wide bandwidths and high coupling efficiencies without the use of bottom reflectors. The measured 1-dB bandwidth is a record 80 nm, and the measured peak coupling efficiency is -1.3 dB, which is competitive with the best Si-only grating couplers. The grating couplers are integrated in a Si(3)N(4) on silicon-on-insulator (SOI) integrated optics platform with aligned waveguides in both the Si(3)N(4) and Si, and we demonstrate a 1 × 4 tunable multiplexer/demultiplexer using the Si(3)N(4)-on-SOI dual-level grating couplers and thermally-tuned Si microring resonators.

Facile synthesis of brush poly(phosphoamidate)s via one-pot tandem ring-opening metathesis polymerization and atom transfer radical polymerization.

Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA)-based brush poly(phosphoamidate)s are successfully synthesized by a combination of ring-opening metathesis polymerization (ROMP) and atom transfer radical polymerization (ATRP) following either a commutative two-step procedure or a straightforward one-pot process using Grubbs ruthenium-based catalysts for tandem catalysis. Compared with the traditional polymerization method, combining ROMP and ATRP in a one-pot process allows the preparation of brush copolymers characterized by a relatively moderate molecular weight distribution and quantitative conversion of monomer. Moreover, the surface morphologies and aggregation behaviors of these polymers are studied by AFM and TEM measurements.

Facile synthesis of thiol-functionalized long-chain highly branched ROMP polymers and surface-decorated with gold nanoparticles.

The synthesis of thiol-functionalized long-chain highly branched polymers (LCHBPs) has been accomplished in combination of ring-opening metathesis polymerization (ROMP) and thiol-Michael addition click reaction. A monotelechelic polymer with a terminal acrylate and many pendent thiol groups is first prepared through adding an internal cis-olefin terminating agent to the reaction mixture immediately after the completion of the living ROMP, and then utilized as an ABn -type macromonomer in subsequent thiol-ene reaction between acrylate and thiol, yielding LCHBPs as the reaction time prolonged. Au nanoparticles are then covalently conjugated onto the surface of thiol-functionalized LCHBP to fabricate novel hybrid nanostructures, which is shown as one interesting application of such functionalized metathesis polymers. This facile approach can be extended toward the fabrication of novel nanomaterials with sophisticated structures and tunable multifunctionalities.

Bio-polyols based waterborne polyurethane coatings reinforced with chitosan-modified ZnO nanoparticles.

The development of environmentally friendly waterborne polyurethane (WPU) coatings from bio-based polyols has received much attention due to increasing environmental concern and the depletion of petroleum resources. In this study, the WPU coatings derived from castor oil and soy polyol were modified by chain extender [bis(2-hydroxyethyl)amino]-methyl-phosphonic acid dimethyl ester. The effect of chitosan-modified ZnO (CS-ZnO) nanoparticles content on the properties of WPU/CS-ZnO coatings and their films were systematically investigated. The results indicated that WPU/CS-ZnO coatings displayed excellent storage stability and the particle sizes firstly decreased and then increased with CS-ZnO loading. CS-ZnO could improve tensile strength and Young's modulus but reduce the optical transparency of WPU/CS-ZnO films. CS-ZnO has a prominent reinforcement effect on the WPU/CS-ZnO matrix. With the addition of 2 wt% CS-ZnO, the tensile strength and Young's modulus of the WPU/CS-ZnO2 film reached 13.4 and 112.1 MPa, 1.68 and 2.6 times over neat WPU film, respectively. TGA results showed that the thermal stability of WPU/CS-ZnO films improved with increased CS-ZnO content. Furthermore, the WPU/CS-ZnO films' wettability decreased with the introduction of CS-ZnO. This work provides a simple and efficient strategy for preparing environmentally friendly bio-based WPU coatings, which are promising for application in the surface coating industry.

Evaluation of the anti-biofilm effect of poloxamer-based thermoreversible gel of silver nanoparticles as a potential medication for root canal therapy.

The purpose of this study was to design silver nanoparticles (AgNPs) poloxamer thermoreversible gel (AgNPs-PL) and investigate whether this gel could provide sustained antibacterial activity against Enterococcus faecalis (E. faecalis) in the root canal. The gels fabricated were characterized in terms of gelatin temperature, particle size, in-vitro Ag+ release, and elemental content. Cytotoxicity of AgNPs-PL on primary human periodontal ligament fibroblasts (HPDLFs) was examined by CCK-8 assay. Characterization of AgNPs-PL gel revealed that it contained particles existing as large clumps/fused aggregates of different shapes, with a mean diameter of 21.624 ± 14.689 nm, exhibited sustained release of Ag+ for 9 days, and non-toxic to HPDLFs at a low dose (4-32 µg/mL) through 24, 48, and 72 h exposures. The antibacterial effect of 16 and 32 µg/mL concentrations of AgNPs-PL was compared with blank poloxamer gel (PL) and calcium hydroxide (CH) using three methods: (I) agar counting plate, (II) scanning electron microscope (SEM) observations, and (III) confocal laser scanning microscope (CLSM) analysis. AgNPs-PL at the two doses above was more effective than PL and CH in removing E. faecalis biofilm at 1, 3, 9 days. Thus, AgNPs-PL exhibits strong activity against E. faecalis and is easy to produce, with a continuous release profile of Ag+. AgNPs-PL gel may be a candidate for a new root canal disinfection.

Tensile force-induced PDGF-BB/PDGFRß signals in periodontal ligament fibroblasts activate JAK2/STAT3 for orthodontic tooth movement.

Orthodontic force-induced osteogenic differentiation and bone formation at tension side play a pivotal role in orthodontic tooth movement (OTM). Platelet-derived growth factor-BB (PDGF-BB) is a clinically proven growth factor during bone regeneration process with unclear mechanisms. Fibroblasts in periodontal ligament (PDL) are considered to be mechanosensitive under orthodontic force. Thus, we established OTM model to investigate the correlation between PDGF-BB and fibroblasts during bone regeneration at tension side. We confirmed that tensile force stimulated PDL cells to induce osteogenic differentiation via Runx-2, OCN up-regulation, and to accelerate new bone deposition along the periodontium and the alveolar bone interface. Interestingly, PDGF-BB level was remarkably enhanced at tension side during OTM in parallel with up-regulated PDGFRß+/α-SMA+ fibroblasts in PDL by immunohistochemistry. Moreover, orthodontic force-treated primary fibroblasts from PDL were isolated and, cultured in vitro, which showed similar morphology and phenotype with control fibroblasts without OTM treatment. PDGFRß expression was confirmed to be increased in orthodontic force-treated fibroblasts by immunofluorescence and flow cytometry. Bioinformatics analysis identified that PDGF-BB/PDGFRß signals were relevant to the activation of JAK/STAT3 signals. The protein expression of JAK2 and STAT3 was elevated in PDL of tension side. Importantly, in vivo, the treatment of the inhibitors (imatinib and AG490) for PDGFRß and JAK-STAT signals were capable of attenuating the tooth movement. The osteogenic differentiation and bone regeneration in tension side were down-regulated upon the treatment of inhibitors during OTM. Meanwhile, the expressions of PDGFRß, JAK2 and STAT3 were inhibited by imatinib and AG490. Thus, we concluded that tensile force-induced PDGF-BB activated JAK2/STAT3 signals in PDGFRß+ fibroblasts in bone formation during OTM.

Thermodynamic analysis of nylon nucleic acids.

The stability and structure of nylon nucleic acid duplexes with complementary DNA and RNA strands was examined. Thermal denaturing studies of a series of oligonucleotides that contained nylon nucleic acids (1-5 amide linkages) revealed that the amide linkage significantly enhanced the binding affinity of nylon nucleic acids towards both complementary DNA (up to 26 degrees C increase in the thermal transition temperature (T(m)) for five linkages) and RNA (around 15 degrees C increase in T(m) for five linkages) compared with nonamide linked precursor strands. For both DNA and RNA complements, increasing derivatization decreased the melting temperatures of uncoupled molecules relative to unmodified strands; by contrast, increasing lengths of coupled copolymer raised T(m) from less to slightly greater than T(m) of unmodified strands. Thermodynamic data extracted from melting curves and CD spectra of nylon nucleic acid duplexes were consistent with loss of stability due to incorporation of pendent groups on the 2'-position of ribose and recovery of stability upon linkage of the side chains.

Concentrations, spatial distributions, and congener profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans around original plastic solid waste recovery sites in China.

The concentrations, profiles, and spatial distributions of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in soil and sediment samples from several typical plastic solid waste (PSW) recovery sites (particularly from areas in which PSW is burned openly) in China were investigated. The results showed that burning PSW directly influenced PCDD/F concentrations immediately around the burning area. All of the samples in which soil contained black burning residue, collected from immediately around burning areas, had PCDD/F concentrations (mean 21708 ng kg-1) and toxic equivalent (TEQ) concentrations (mean 2140 ng I-TEQ kg-1 or 1877 ng WHO2006-TEQ kg-1) more than 100 times higher than the concentrations in samples collected away from burning areas (mean 222 ng kg-1, 8.75 ng I-TEQ kg-1, 7.96 ng WHO2006-TEQ kg-1). Principal component analysis and hierarchical cluster analysis indicated that the PCDD/F concentrations in seven soil samples from near PSW burning areas were influenced by PSW burning but that the PCDD/Fs in these soil samples may have had other or multiple sources. PCDD/F distributions at PSW recovery sites have been investigated in few previous studies. The results presented here indicate that appropriate measures should be taken to decrease the ecological risks posed by PSW recovery and to prevent, control, and remediate PCDD/F and other chemical contamination caused by PSW recovery.

Health safety of main water pipe materials supplied in China market.

OBJECTIVE: To assess the health safety of copper, steel and plastic water pipes by field water quality investigations. METHODS: Four consumers were randomly selected for each type of water pipes. Two consumers of every type of the water pipes had used the water pipes for more than 1 year and the other 2 consumers had used the water pipes for less than 3 months. The terminal volume of tap water in copper and steel water pipes should be not less than 0.1 liter, whereas that in plastic water pipes should be not less than 1 liter. RESULTS: The mean values of the experimental results in the second field water quality investigation of the copper and steel water pipes met the Sanitary Standards for Drinking Water Quality. The items of water sample of the plastic water pipes met the requirements of the Sanitary Standards for Drinking Water Quality. CONCLUSION: Copper, steel, and plastic pipes can be used as drinking water pipes.

Porous magnesium loaded with gentamicin sulphate and in vitro release behavior.

Our aim was to develop a biocompatible bone repair material that has the advantage of preventing postoperative infections. Finally, the porous magnesium (p-Mg) loaded with gentamicin sulphate (GS-loaded Mg-G) was fabricated. The GS release behavior of the GS-loaded Mg-G in phosphate buffer saline (PBS) was investigated. The effective release time of GS reached to 14days. In addition, the effects of porosity and pore diameter of p-Mg on the GS release behavior of the GS-loaded Mg-G were studied. In the initial burst release stage, the GS release rate of the GS-loaded Mg-G increased with the increasing porosity or the increasing pore diameter of p-Mg. The GS-loaded Mg-G with larger original pore diameter has higher burst release of GS. Moreover, the in vitro antibacterial test of the GS-loaded Mg-G indicated that this biomaterial has obvious antibacterial effect. This study can provide information for p-Mg loaded with drug(s) as functional bone repair materials with drug-delivery capabilities.