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Complex coacervation is an electrostatically-driven phase separation phenomenon that is utilized in a wide range of everyday applications and is of great interest for the creation of self-assembled materials. Here, we utilized turbidity to characterize the effect of salt type on coacervate formation using two vinyl polyelectrolytes, poly(acrylic acid sodium salt) (pAA) and poly(allylamine hydrochloride) (pAH), as simple models for industrial and biological coacervates. We confirmed the dominant role of salt valence on the extent of coacervate formation, while demonstrating the presence of significant secondary effects, which can be described by Hofmeister-like behavior. These results revealed the importance of ion-specific interactions, which are crucial for the informed design of coacervate-based materials for use in complex ionic environments, and can enable more detailed theoretical investigations on the role of subtle electrostatic and thermodynamic effects in complex coacervation.

Tissue adhesives are regularly used for wound healing, bleeding control and sealing internal organ leakages. However, currently available tissue adhesives are often cytotoxic. Polycations containing primary amines are generally known to induce cytotoxicity. Complex coacervates, composed of oppositely charged polyelectrolytes, may offer a biocompatible alternative. In this study, primary amines of polyallylamine hydrochloride (pAH) were reacted with glycidyltrimethylammonium chloride (GTMAC) following an epoxide ring nucleophilic substitution to obtain pAH with quaternary ammonium pendant groups (q-pAH). These polycations were combined with negatively charged polysulfopropyl methacrylate (pSPMA) to form complex coacervates. The biocompatibility of the individual polyelectrolytes and resulting complex coacervates was studied using A549 cells through Live/Dead, MTS (3-(4,5-dimethylthiazol-2-yl)-5-(3-carboxymethoxyphenyl)-2-(4-sulfophenyl)-2H-tetrazolium) and LDH (lactate dehydrogenase) assays. Additionally, adhesion to porcine tissues was evaluated. Quaternization of pAH strongly reduced the critical salt concentration (CSC) of the coacervate system, while remaining easy to process and injectable. The cytocompatibility of q-pAH/pSPMA was increased compared to pAH/pSPMA, mainly caused by the reduction of the required salt concentration. Nevertheless, quaternization did not reduce the cytotoxicity of the polycation itself. Complexation with pSPMA effectively reduced cytotoxicity through charge neutralization. Upon direct contact of A549 cells with q-pAH/pSPMA coacervates improved biocompatibility was observed compared to pAH/pSPMA, which could not be fully attributed to effects of reduced salt levels. Both coacervates formed stable, gel-like patches upon the salt switch and these adhered to various tissues. Reduction of complex coacervate cytotoxicity by polycation quaternization can be included in future designs of medical adhesives. Graphical Abstract

In this work we have investigated the effect of surface modification of fibres on the overall mechanical properties of high-density papers. Paper sheets were prepared by a combination of heat-pressing and polyelectrolyte Layer-by-Layer (LbL) modification of different softwood fibres. LbLs of Polyallylamine Hydrochloride (PAH) and Hyaluronic Acid (HA) were adsorbed onto unbleached kraft fibres and bleached Chemo-ThermoMechanical Pulp (CTMP) to improve the strength of the fibre–fibre joints in papers made from these fibres. Additionally, different sheet-making procedures were used to prepare a range of network densities with different degrees of fibre–fibre interaction in the system. The results demonstrate that interfacial adhesion within fibre–fibre joints plays a pivotal role in the network's performance, even at higher paper densities. Hygroexpansion measurements and fracture zone imaging with Scanning Electron Microscopy (SEM) further support the claim that stronger interactions between the fibres allow for a better utilisation of the inherent fibre properties. Surface treatments and network densification significantly improved the paper sheets' mechanical properties. Specifically, LbL-treatments alone increased specific stiffness up to 60% and specific strength by over 100%. This improvement is linked to the build-up of residual stresses during drying. Due to a high interaction between the fibres during water removal the fibres become constrained, leading to increased stretching of fibre segments. Strengthened fibre joints intensify this constraint, further increasing the stretch and, consequently, the paper's strength.

Residential wood burning contributes to the total atmospheric aerosol burden; however, large uncertainties remain in the magnitude and characteristics of wood burning products. Primary emissions are influenced by a variety of parameters, including appliance type, burner wood load and wood type. In addition to directly emitted particles, previous laboratory studies have shown that oxidation of gas-phase emissions produces compounds with sufficiently low volatility to readily partition to the particles, forming considerable quantities of secondary organic aerosol (SOA). However, relatively little is known about wood burning SOA, and the effects of burn parameters on SOA formation and composition are yet to be determined. There is clearly a need for further study of primary and secondary wood combustion aerosols to advance our knowledge of atmospheric aerosols and their impacts on health, air quality and climate. For the first time, smog chamber experiments were conducted to investigate the effects of wood loading on both primary and secondary wood combustion products. Products were characterized using a range of particle- and gas-phase instrumentation, including an aerosol mass spectrometer (AMS). A novel approach for polycyclic aromatic hydrocarbon (PAH) quantification from AMS data was developed and results were compared to those from GC-MS analysis of filter samples. Similar total particle mass emission factors were observed under high and average wood loadings; however, high fuel loadings were found to generate significantly higher contributions of PAHs to the total organic aerosol (OA) mass compared to average loadings. PAHs contributed 15 ± 4% (mean ±2 sample standard deviations) to the total OA mass in high-load experiments, compared to 4 ± 1% in average-load experiments. With aging, total OA concentrations increased by a factor of 3 ± 1 for high load experiments compared to 1.6 ± 0.4 for average-load experiments. In the AMS, an increase in PAH and aromatic signature ions at lower m / z values, likely fragments from larger functionalized PAHs, was observed with aging. Filter samples also showed an increase in functionalized PAHs in the particles with aging, particularly oxidized naphthalene species. As PAHs and their oxidation products are known to have deleterious effects on health, this is a noteworthy finding to aid in the mitigation of negative wood burning impacts by improving burner operation protocols.

Magnetic nanoparticles (MNPs) hold significant potential for a wide range of applications, however, surface modification or bio-conjugation of MNPs often leads to their aggregation and instability. To address this, we proposed a facile method using a layer-by-layer (LbL) coating technique with polyallylamine hydrochloride (PAH) and poly(styrene sulfonic acid) sodium salt (PSS), so as to maintain the dispersion stability and functionality of MNPs. This method enabled us to develop the powerful MNPs towards to their use in the electrochemical biosensor, by combining both the redox probes (ferrocene (Fc), anthraquinone (AQ), or monocarboxymethylene blue (MB)) and bio-probes (IgG). The redox molecules were effectively anchored to the MNPs under the organic solvents, while such functionalized MNPs surface were subsequently protected by the LbL coating process prior to dispersing in high ionic strength solutions (e.g. Phosphate-buffered saline). And the out-layer of polyelectrolyte shell allowed biomolecules to attach to the MNP surface without chemical cross-linking. Our results demonstrated that the TEM size of MNPs@Fc, MNP@AQ and MNP@MB after LbL coating were characterized as 11.0 ± 2.0 nm, 10.5 ± 2.1 nm and 12.4 ± 2.2 nm and these developed redox MNPs of MNPs@Fc, MNPs@AQ and MNPs@MB were characterized by square wave voltammetry (SWV) with their redox intensity of 0.64 ± 0.10 µA, 23.25 ± 0.73 µA and 0.48 ± 0.13 µA, respectively. In addition, the binding efficiency of adsorption between the MNPs and IgG was up to 78%, evidenced by SDS-PAGE gel analysis. This facile method offered a versatile and effective way to functionalize MNPs, combining redox and biological properties for potential applications in disease diagnosis and point-of-care diagnostics.

Here, we report the initial observations of distributions of polycyclic aromatic hydrocarbons (PAH) in subsurface waters near the Deepwater Horizon oil well site (also referred to as the Macondo, Mississippi Canyon Block 252 or MC252 well). Profiles of in situ fluorescence and beam attenuation conducted during 9‐16 May 2010 were characterized by distinct peaks at depths greater than 1000 m, with highest intensities close to the wellhead and decreasing intensities with increasing distance from the wellhead. Gas chromatography/mass spectrometry (GC/MS) analyses of water samples coinciding with the deep fluorescence and beam attenuation anomalies confirmed the presence of polycyclic aromatic hydrocarbons (PAH) at concentrations reaching 189 μg L−1 (ppb). Subsurface exposure to PAH at levels considered to be toxic to marine organisms would have occurred in discrete depth layers between 1000 and 1400 m in the region southwest of the wellhead site and extending at least as far as 13 km.

Wound infections are the main complication when treating skin wounds. This work reports a novel antimicrobial material using green synthesized zinc oxide nanoparticles (ZnONPs) incorporated in polymeric fibers for wound healing purposes. ZnONPs are a promising antimicrobial nanomaterial with high activity against a range of microorganisms, including drug-resistant bacteria. The electrospun fibers were obtained using polyacrylic acid (PAA) and polyallylamine hydrochloride (PAH) and were loaded with ZnONPs green synthesized from Ilex paraguariensis leaves with a spherical shape and ~18 nm diameter size. The fibers were produced using the electrospinning technique and SEM images showed a uniform morphology with a diameter of ~230 nm. EDS analysis proved a consistent dispersion of Zn in the fiber mat, however, particle agglomerates with varying sizes were observed. FTIR spectra confirmed the interaction of PAA carboxylic groups with the amine of PAH molecules. Although ZnONPs presented higher antimicrobial activity against S. aureus than E. coli, resazurin viability assay revealed that the PAA/PAH/ZnONPs composite successfully inhibited both bacteria strains growth. Photomicrographs support these results where bacteria clusters were observed only in the control samples. The PAA/PAH/ZnONPs composite developed presents antimicrobial activity and mimics the extracellular matrix morphology of skin tissue, showing potential for wound healing treatments.

Background: Polycyclic aromatic hydrocarbons (PAHs) are carcinogenic environmental pollutants generated during incomplete combustion. After exposure and during metabolism, PAHs can form reactive epoxides that can covalently bind to DNA. These PAH–DNA adducts are established markers of cancer risk. PAH exposure has been associated with epigenetic alterations, including genomic cytosine methylation. Both global hypomethylation and hypermethylation of specific genes have been associated with cancer and other diseases in humans. Experimental evidence suggests that PAH–DNA adduct formation may preferentially target methylated genomic regions. Early embryonic development may be a particularly susceptible period for PAH exposure, resulting in both increased PAH-DNA adducts and altered DNA methylation. Objective: We explored whether prenatal exposure to PAHs is associated with genomic DNA methylation in cord blood and whether methylation levels are associated with the presence of detectable PAH-DNA adducts. Methods: In a longitudinal cohort study of nonsmoking women in New York City, we measured PAH exposure during pregnancy using personal air monitors, assessed PAH internal dose using prenatal urinary metabolites (in a subset), and quantified benzo[a] pyrene-DNA adducts and genomic DNA methylation in cord blood DNA among 164 participants. Results: Prenatal PAH exposure was associated with lower global methylation in umbilical cord white blood cells (p * 0.05), but global methylation levels were positively associated with the presence of detectable adducts in cord blood (p = 0.01). Conclusions: These observations suggest that PAH exposure was adequate to alter global methylation in our study population. Additional epidemiologic studies that can measure site-specific cytosine methylation and adduct formation will improve our ability to understand this complex molecular pathway in vivo.

Background: In this prospective cohort study of Caucasian mothers and children in Krakow, Poland, we evaluated the role of prenatal exposure to urban air pollutants in the pathogenesis of neurobehavioral disorders. Objectives: The objective of this study was to investigate the relationship between prenatal polycyclic aromatic hydrocarbon (PAH) exposure and child intelligence at 5 years of age, controlling for potential confounders suspected to play a role in neurodevelopment. Methods: A cohort of pregnant, healthy, nonsmoking women was enrolled in Krakow, Poland, between 2001 and 2006. During pregnancy, participants were invited to complete a questionnaire and undergo 48-hr personal air monitoring to estimate their babies' exposure, and to provide a blood sample and/or a cord blood sample at the time of delivery. Two hundred fourteen children were followed through 5 years of age, when their nonverbal reasoning ability was assessed using the Raven Coloured Progressive Matrices (RCPM). Results: We found that higher (above the median of 17.96 ng/m³) prenatal exposure to airborne PAHs (range, 1.8-272.2 ng/m³) was associated with decreased RCPM scores at 5 years of age, after adjusting for potential confounding variables (n = 214). Further adjusting for maternal intelligence, lead, or dietary PAHs did not alter this association. The reduction in RCPM score associated with high airborne PAH exposure corresponded to an estimated average decrease of 3.8 IQ points. Conclusions: These results suggest that prenatal exposure to airborne PAHs adversely affects children's cognitive development by 5 years of age, with potential implications for school performance. They are consistent with a recent finding in a parallel cohort in New York City.

BackgroundCentral nervous system (CNS) tumours are the commonest childhood solid malignancy. We assessed the risk of childhood CNS tumours associated with parental occupational exposure to pesticides, polycyclic aromatic hydrocarbons (PAH), diesel motor exhaust (DME), asbestos, crystalline silica, and metals.MethodsWe pooled three population-based case-control studies from France, Germany and the UK. Cases were children below 15 years of age diagnosed with CNS tumours; controls were matched to cases by gender and age. Socio-demographic and parental occupational information was collected using study-specific standardised interviews, either face-to-face or by telephone. Each study provided occupational data coded according to their national schemes; which were harmonised into ILO's International Standard Classification of Occupations 1968 and 1988. Two general population job-exposure matrices (DOM-JEM, ALOHA+) were used to estimate parental occupational exposures. Odds ratios (ORs) and 95% confidence intervals (CI) were estimated using logistic regression.ResultsThe study included 1,361 children with CNS tumours and 5,500 controls. ORs for paternal exposure (yes/no) around conception were as follows: PAH 1.22 (95% CI: 0.98-1.52); metals 1.18 (95% CI: 0.96-1.46); and asbestos 1.12 (95% CI: 0.95-1.32). Asbestos was the only potentially hazardous exposure were the point estimate increased at higher levels; OR 1.42 (95% CI: 0.87-2.32). Paternal exposure to pesticides, DME and silica showed no increased risk. The prevalence of maternal occupational exposures to pesticides, PAH, DME, asbestos, silica, and metals was low; and no increased ORs were observed either around the time of conception or during pregnancy.ConclusionOur large pooled study provided little evidence of an association between paternal occupational exposure to PAH, metals, and asbestos around conception and CNS tumour risk in the offspring. Previous studies have reported inconsistent results for PAH, while no studies have reported significant associations for asbestos and metals.