Photo-Controlled Polymerization-Induced Self-Assembly (Photo-PISA): A Novel Strategy Using In Situ Bromine-Iodine Transformation Living Radical Polymerization.

A series of hydrophilic poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMA) macroinitiators and stabilizers are synthesized in methanol through in situ photo-controlled bromine-iodine transformation living radical polymerization, where ethyl α-bromophenylacetate (EBPA) is the initial initiator and is converted to an iodo-type initiator in the presence of NaI. The subsequent photo-controlled polymerization-induced self-assembly (photo-PISA) process is achieved by adding a second monomer, hydrophobic benzyl methacrylate (BnMA), under irradiation with blue light emitting diode (LED) light at room temperature. The effect of the target degree of polymerization (DP) of PPEGMA, PBnMA, as well as the solids content on the self-assembly behavior of block copolymer PPEGMA-b-PBnMA is evaluated by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) spectroscopy, transmission electron microscopy (TEM), and dynamic light scattering (DLS) characterization. Resulting uniform spherical micelles and vesicle aggregates are observed.

Bioconjugation and Fluorescence Labeling of Iron Oxide Nanoparticles Grafted with Bromomaleimide-Terminal Polymers.

Iron oxide nanoparticles have been widely applied in biomedical applications for their unique physical properties. Despite the relatively mature synthetic approaches for iron oxide nanoparticles, surface modification strategies for obtaining particles with satisfactory biofunctionality are still urgently needed to meet the challenge of nanomedicine. Herein, we report a surface modification and biofunctionalization strategy for iron oxide-based magnetic nanoparticles based on a dibromomaleimide (DBM)-terminated polymer with brushed polyethylene glycol (PEG) chains. PEG acrylate and phosphonate monomers, serving as antibiofouling and surface anchoring compartments for iron oxide nanoparticles, were incorporated utilizing a novel DBM containing reversible addition-fragmentation chain transfer (RAFT) agent. The particles prepared through this new surface architecture possessed high colloidal stability in a physiological buffer and the capacity of covalent conjugation with biomolecules for targeting. Cell tracking of the molecular probes was achieved concomitantly by exploiting DBM conjugation-induced fluorescence of the nanoparticles.

One-Pot Synthesis of Thermoresponsive Amyloidogenic Peptide-Polymer Conjugates via Thio-Bromo "Click" Reaction of RAFT Polymers.

A synthetic strategy to efficiently prepare main-chain peptide-polymer conjugates probing their aggregation in solution is described. An in situ tandem reaction based on aminolysis/thio-bromo "click" reaction is performed to tether an amyloidogenic peptide fragment amyloid-ß17-20 (Leu-Val-Phe-Phe (LVFF)) to the ω-chain end of poly(diethylene glycol methyl ether acrylate) (PDEGA), prepared via reversible addition fragmentation chain transfer polymerization. Structural confirmation of the constructed conjugates PDEGA-LVFF (Mn,SEC = 5600, Ð = 1.21), (Mn,SEC = 7600, Ð = 1.16), and (Mn,SEC = 8900, Ð = 1.15) is successfully made by combined studies of 1 H NMR, size-exclusion chromatography, matrix-assisted laser desorption ionization time-of-flight (MALDI-TOF) mass spectrometry, and electrospray ionization time-of-flight (ESI-TOF) mass spectrometry. The effect of the peptidic constituent on the thermoresponsive behavior of the polymer is examined by UV-vis spectroscopy, and the self-assembly behavior of the amphiphilic conjugate is further exploited, exhibiting micellar morphology in aqueous solution.

Identification of Novel Brominated Compounds in Flame Retarded Plastics Containing TBBPA by Combining Isotope Pattern and Mass Defect Cluster Analysis.

The study of not only main flame retardants but also of related degradation products or impurities has gained attention in the last years and is relevant to assess the safety of our consumer products and the emission of potential contaminants into the environment. In this study, we show that plastics casings of electric/electronic devices containing TBBPA contain also a complex mixture of related brominated chemicals. These compounds were most probably coming from impurities, byproducts, or degradation products of TBBPA and TBBPA derivatives. A total of 14 brominated compounds were identified based on accurate mass measurements (formulas and tentative structures proposed). The formulas (or number of bromine elements) for 19 other brominated compounds of minor intensity are also provided. A new script for the recognition of halogenated compounds based on combining a simplified isotope pattern and mass defect cluster analysis was developed in R for the screening. The identified compounds could be relevant from an environmental and industrial point of view.

N-bromo-dimethylhydantoin polystyrene resin for water microbial decontamination.

N-bromo-dimethylhydantoin polystyrene beads were synthesized and tested as antimicrobial agents for water microbial decontamination. Optimization of synthetic process was thoroughly investigated, including solvents used, ratio of reactants and reaction conditions, kilogram scale production, and detailed spectral analysis. The microbial inactivation efficiency was studied according to the NSF-231 Guide Standard and Protocol for Testing Microbiological Water Purifiers against Escherichia coli and MS2 phage. The tested resins maintained their activity for 550 L. Thus, N-bromo-dimethylhydantoin-polystyrene beads synthesized under optimized conditions at kilogram quantities have a potential use in water purification filters.

GC separation of enantiomers of alkyl esters of 2-bromo substituted carboxylic acids enantiomers on 6-TBDMS-2,3-di-alkyl- ß- and γ-cyclodextrin stationary phases.

The gas chromatographic separation of enantiomers of 2-Br carboxylic acid derivatives was studied on four different 6-TBDMS-2,3-di-O-alkyl- ß- and -γ-CD stationary phases. The differences in thermodynamic data {ΔH and -ΔS} for the 15 structurally related racemates were evaluated. The influence of structure differences in the alkyl substituents covalently attached to the stereogenic carbon atom, as well as in the ester group of the homologous analytes, and the selectivity of modified ß- and γ- cyclodextrin derivatives was studied in detail. The cyclodextrin cavity size, as well as elongation of alkyl substituents in positions 2 and 3 of 6-TBDMS-ß-CD, also affected their selectivity. The quality of enantiomeric separations is influenced mainly by alkyl chains of the ester group of the molecule and this appears to be independent of the CD stationary phase used. In some cases the separations occur as the result of external adsorption rather than inclusion complexations with the chiral selector. It was found that the temperature dependencies of the selectivity factor were nonlinear.

A novel subcritical water synergistic co-treatment of brominated epoxy resin and copper-based spent catalysts: debromination, phenol production, and copper recovery.

In this study, a high-efficiency co-treatment strategy for brominated epoxy resin (BER) and copper-based spent catalyst (CBSC) was developed by using subcritical water (SubCW) process. Multivalent species of copper released from CBSC could accelerate the electron transfer of the SubCW system and efficiently catalyze radical reactions to promote the debromination and decomposition of BER, and had an effect on the capture and binding of bromine species. Meanwhile, the formation of HBr by the BER debromination resulted in a decrease in the system pH and markedly enhanced the leaching/recovery of Cu from CBSC. The optimal conditions of the SubCW co-treatment process were as follows: reaction temperature of 350 °C, solid-to-liquid ratio of 1:30 g/mL, BER-to-CBSC mass ratio of 10:1 g/g, and reaction time of 60 min. Under the optimal conditions, 97.12 % of the Br could be removed from BER by the SubCW co-treatment process and a high-purity phenol (64.09 %) could be obtained in the oil phase product, and 86.44 % of Cu in the CBSC could be leached and recovered. The introduction of CBSC significantly changed the decomposition path of BER. Compared to the SubCW process without CBSC, bromine-free oils products could be obtained by the co-treatment process of BER and CBSC at low-temperature. This study provided a novel understanding of resource conversion mechanism of BER and CBSC in subcritical water medium via the synergistic effect between the two different waste streams to improve treatment efficiency and synchronously recover high-value products.

The Ebola virus matrix protein deeply penetrates the plasma membrane: an important step in viral egress.

Ebola virus, from the Filoviridae family has a high fatality rate in humans and nonhuman primates and to date, to the best of our knowledge, has no FDA approved vaccines or therapeutics. Viral protein 40 (VP40) is the major Ebola virus matrix protein that regulates assembly and egress of infectious Ebola virus particles. It is well established that VP40 assembles on the inner leaflet of the plasma membrane; however, the mechanistic details of VP40 membrane binding that are important for viral release remain to be elucidated. In this study, we used fluorescence quenching of a tryptophan on the membrane-binding interface with brominated lipids along with mutagenesis of VP40 to understand the depth of membrane penetration into lipid bilayers. Experimental results indicate that VP40 penetrates 8.1 Å into the hydrocarbon core of the plasma membrane bilayer. VP40 also induces substantial changes to membrane curvature as it tubulates liposomes and induces vesiculation into giant unilamellar vesicles, effects that are abrogated by hydrophobic mutations. This is a critical step in viral egress as cellular assays demonstrate that hydrophobic residues that penetrate deeply into the plasma membrane are essential for plasma membrane localization and virus-like particle formation and release from cells.

Local control of protein binding and cell adhesion by patterned organic thin films.

Control of the cell adhesion and growth on chemically patterned surfaces is important in an increasing number of applications in biotechnology and medicine, for example implants, in-vitro cellular assays, and biochips. This review covers patterning techniques for organic thin films suitable for site-directed guidance of cell adhesion to surfaces. Available surface patterning techniques are critically evaluated, with special emphasis on surface chemistry that can be switched in time and space during cultivation of cells. Examples from the authors' laboratory include the use of cell-repellent self-assembled monolayers (SAM) terminated by oligoethylene glycol (OEG) units and the lifting of the cell repellent properties by use of electrogenerated Br2/HOBr which can be performed with positionable microelectrodes. Structural changes of the SAM were analyzed by polarization-modulated infrared reflection absorption spectroscopy (PM IRRAS). Use of a soft array system of individually addressable microelectrodes enables formation of flexible and complex patterns in a short time and has the potential for further acceleration of probe-induced local manipulation of cell adhesion.

Design and synthesis of new 1D and 2D R-isophthalic acid-based coordination polymers (R = hydrogen or bromine).

Three new R-isophthalic acid-based (R = H or Br) coordination polymers have been designed and synthesized. By changing the N-containing ligand in the system, we are able to tune the dimensionality of coordination polymers from one-dimension (1D) to two-dimensions (2D) with the same basic building unit. Also, different metal ions can be incorporated into the same structures. Compound 1 [Cu(bipa)(py)2]·0.5(H2O) (H2bipa = 5-bromoisophthalic acid; py = pyridine) and compound 2 [Co(bipa)(py)2] are 1D chain structures. Compound 3 [Cu8(ipa)8(bpe)8]·2(bpe)·4(H2O) (bpe=1,2-bis(4-pyridyl)ethane) is a 2D layered structure.

Leaching behavior of Sb and Br from E-waste flame retardant plastics.

The improper disposal of E-waste flame retardant plastics laden with antimony (Sb) and bromine (Br) has brought enormous environmental hazards, however, rare information on the effective removal of Sb and Br is available. In this study, through building an alkaline sulfide system under hydrothermal conditions, Sb and Br were simultaneously extracted from flame retardant plastic with high efficiency of 85.60% and 90.13%, respectively. Sulfur ion through mass transfer reacted with encapsulated Sb2O3 to form safe and non-toxic SbS33-. Alkaline solution trapped the Br through substitution or neutralization reaction to inhibit the formation of brominated organic compounds. The results showed that the optimum temperature, residence time, Na2S and NaOH concentration for hydrothermal removal of Sb and Br were 220 °C, 2 h, 50 g/L and 20 g/L. The results also revealed that both Na2S and NaOH played an interrelated role in the process of Sb removal. However, NaOH was the only factor controlling the process of debromination. Moreover, the FTIR structure of plastic after alkaline sulfide hydrothermal treatment remained unchanged, which implies that the treated plastic can be reused, and is an added advantage of this technology. The TG-DTG analysis proved the effectiveness of alkaline sulfide hydrothermal treatment in removing Sb and Br.

Br-rich tips of calcified crab claws are less hard but more fracture resistant: a comparison of mineralized and heavy-element biological materials.

We find that the spoon-like tips of the chelipeds (large claws) of the crab Pachygrapsus crassipes differ from the rest of the claw in that they are not calcified, but instead contain about 1% bromine--thus they represent a new example of a class of structural biological materials that contain heavy elements such as Zn, Mn, Fe, Cu, and Br bound in an organic matrix. X-ray absorption spectroscopy data suggest that the bromine is bound to phenyl rings, possibly in tyrosine. We measure a broad array of mechanical properties of a heavy-element biological material for the first time (abrasion resistance, coefficient of kinetic friction, energy of fracture, hardness, modulus of elasticity and dynamic mechanical properties), and we make a direct comparison with a mineralized tissue. Our results suggest that the greatest advantage of bromine-rich cuticle over calcified cuticle is resistance to fracture (the energy of fracture is about an order of magnitude greater than for calcified cuticle). The greatest advantage relative to unenriched cuticle, represented by ant mandible cuticle, is a factor of about 1.5 greater hardness and modulus of elasticity.The spoon-like tips gain additional fracture resistance from the orientation of the constituent laminae and from the viscoelasticity of the material. We suggest that fracture resistance is of greater importance in smaller organisms, and we speculate that one function of heavy elements in structural biological materials is to reduce molecular resonant frequencies and thereby increase absorption of energy from impacts.

Facile functionalization of multilayer fullerenes (carbon nano-onions) by nitrene chemistry and "grafting from" strategy.

Facile functionalization of multilayer fullerenes (carbon nano-onions, CNOs) was carried out by [2+1] cycloaddition of nitrenes. The products were further derivatized by using the "grafting from" strategy of in situ ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP). Using one-step nitrene chemistry with high-energy reagents, such as azidoethanol and azidoethyl 2-bromo-2-methyl propanoate, in N-methyl-2-pyrrolidone at 160 degrees C for 16 h, hydroxyl and bromide functionalities were introduced onto the surfaces of CNOs. These hydroxyl CNOs (CNO-OH) and bromic CNOs (CNO-Br) were extensively characterized by various techniques such as thermal gravimetric analysis (TGA), transmission electron microscopy (TEM), Raman spectroscopy and X-ray photo electron spectroscopy (XPS). TGA measurements indicated that the surface hydroxyl and bromide group density reached 1.49 and 0.49 mmol g(-1), respectively. The as-functionalized CNOs showed much better solubility in solvents than pristine CNOs. The CNO-OH were also observed to fluoresce at lambda = 453 nm in water. The CNO-OH and CNO-Br can be conveniently utilized as macroinitiators to conduct surface-initiated in-situ polymerizations. Poly(epsilon-caprolactone) (PCL, 45 wt%) and polystyrene (PS, 60 wt%) were then grafted from surfaces of CNOs through the ROP of epsilon-caprolactone with the macroinitiator CNO-OH and the ATRP of styrene with the macroinitiator CNO-Br, respectively. The structures and morphology of the resulting products were characterized by (1)H NMR, scanning electron microscopy (SEM), TEM, and atomic force microscopy (AFM). The polymer functionalized CNOs have good solubility/dispersibility in common organic solvents. The facile and scalable functionalization approaches can pave the way for the comprehensive investigation of chemistry of CNOs and fabrication of novel CNO-based nanomaterials and nanodevices.

Bromine and iodine determination in human saliva: Challenges in the development of an accurate method.

In this work, an analytical method for bromine and iodine determination in human saliva was proposed. A simple protocol based on centrifugation and direct analysis of supernatant by inductively coupled plasma mass spectrometry (ICP-MS) was investigated. Although this method was feasible for bromine determination, iodine was partially present in the supernatant and an agreement about 54% with reference value was obtained. In addition, microwave-induced combustion (MIC) and microwave-assisted dissolution were also evaluated. Using MIC, 0.2 mL of saliva added on 300 mg of microcrystalline cellulose were efficiently digested. A diluted solution (50 mmol L-1 NH4OH) was used for analytes absorption, and a reflux step of 5 min was applied to ensure quantitative recoveries of Br and I. Accuracy was evaluated by analyte recovery experiments, and recoveries between 94% and 98% were obtained. Microwave-assisted dissolution was evaluated for 2.0 mL of saliva using also a diluted alkaline solution (25 mmol L-1 NH4OH) and a microwave irradiation program of 35 min (including the cooling step). Results for this method agreed with those obtained using MIC. Although MIC has also been appropriated for further determination of Br and I in saliva, microwave-assisted dissolution can be considered a simpler sample preparation method and it was effective for high amount of sample (up to 2.0 mL). Moreover, final solutions were compatible with ICP-MS analysis, allowing the quantification of Br and I in human saliva at ultra-trace concentrations (limits of quantification were 0.052 µg mL-1 for Br and 0.022 µg mL-1 for I).

New radiopaque acrylic bone cement. II. Acrylic bone cement with bromine-containing monomer.

Bromine-containing methacrylate, 2-(2-bromopropionyloxy) ethyl methacrylate (BPEM), had been used in the formulation of acrylic radiopaque cements. The effect of this monomer incorporated into the liquid phase of acrylic bone cement, on the curing parameters, thermal properties, water absorption, density, compression tests and radiopacity was studied. A decrease of maximum temperature and an increase of the setting time were observed with the addition of the bromine-containing monomer in the radiolucent cement composition. Adding BPEM in radiolucent acrylic bone cements composition results in the decrease of glass transition temperature and increase of its thermal stability. Acrylic bone cements modified with bromine-containing comonomer are characterized by polymerization shrinkage lower than the radiolucent cement. Addition of bromine-containing comonomer in radiolucent acrylic bone cement composition determines the increase of compressive strength. Acrylic bone cements modified with bromine-containing comonomer proved to be radiopaque.

WEEE plastic sorting for bromine essential to enforce EU regulation.

The plastics of waste of electric and electronic equipment (WEEE) are improved for fire safety by flame retardants, and particularly brominated flame retardants (BFR). As waste, the management of these plastic fractions must comply with the update of the regulation of waste hazard classification (2014, 2017), the publication of a technical standard on management of WEEE (2015), and a restriction of use for decabromodiphenylether in the product regulation (2017). Data of bromine (n=4283) and BFR concentrations (n=98) in plastics from electric and electronic equipment (EEE), and from WEEE processing facilities before and after sorting for bromine in four sites in France have been studied for chemical composition and for regulatory classification. The WEEE was analysed by handheld X-ray fluorescence, and the waste was sorted after shredding, by on-line X-ray transmission for total bromine content (< or > 2000 mg/kg) in small household appliances (SHA), cathode ray tubes (CRT) and flat screens plastics. In equipment (n=347), 15% of the equipment items have no bromine, while 46% have at least one part with bromine, and 39% have all parts brominated. The bromine concentration in plastics is very heterogeneous, found in high concentrations in large household appliance (LHA) plastics, and also found in unexpected product categories, as observed by other authors. Clearly, an unwanted global loop of brominated substances occurs via the international recycling of plastic scrap. In waste (n=65), polybromobiphenyls, polybromodiphenylethers (PBDE), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane were analysed. The most concentrated BFRs are decaBDE (3000 mg/kg) and TBBPA (8000 mg/kg). The bromine concentration of regulated brominated substances was identified in 2014 and 2015 to be up to 86% of total bromine in "old" waste (SHA, CRT), 30-50% in "younger" waste (Flat screens), and a mean of only 8% in recent products (2009-2013). Regulated substances are a minority of all the brominated substances and the only practical way to sort is to measure total bromine on-line. The sorting reduces the mean bromine concentration in the "Low Br" fraction in all sites, and reduces the decaBDE concentration to levels below the restricted use limit. After sorting, the concentration in the "High Br" fractions exceeds all present or future regulatory limits. In conclusion, sorting of small household appliances, cathode ray tubes and flat screen plastics is necessary to avoid uncontrolled dispersion of regulated substances in recycled raw material. Other categories (large household appliances, electric and electronic tools, lighting equipment) should also be considered, since their total bromine content (unweighted mean concentration) is high for some of these products. A European campaign consisting of 7 countries and 35 sites will begin in 2017, directed by WEEE Forum, the European association speaking for thirty-one not-for-profit e-waste producer responsibility organisations, to assess the mean bromine content of plastics from large household appliances after shredding.

CO2-Triggered microreactions in liquid marbles.

On-demand initiation of dual- and multi-component microreactions inside liquid marbles (LMs) was developed by coalescing contacting patchy LMs containing separate reagents through CO2-induced wetting transition of the interface between the LMs.

Polymer brushes in nanopores surrounded by silicon-supported tris(trimethylsiloxy)silyl monolayers.

A chemically grafted tris(trimethylsiloxy)silyl (tris(TMS)) monolayer on a silicon oxide substrate was used as a template for creating nanoclusters of polymer brushes. Polymer brushes were synthesized by surface-initiated polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) and tert-butyl methacrylate (t-BMA) via atom transfer radical polymerization (ATRP) from alpha-bromoester groups tethered to the residual silanol groups on the silicon surface after generating a range of tris(TMS) coverage. CuBr/bpy and CuBr/PMDETA were used as the catalytic system for PMPC and Pt-BMA synthesis, respectively. The percentage of tris(TMS) coverage significantly influenced the thickness and morphology of the polymer brushes. Protrusions representing self-aggregation of PMPC brushes in nanopores as visualized by AFM analysis evidently suggested that PMPC brushes were distributed nanoscopically on the surface. The protrusion size and surface roughness corresponded quite well with the graft density of PMPC brushes. The fact that Pt-BMA brushes grown from nanopores were almost featureless implies that self-aggregation of PMPC brushes is truly a consequence of phase incompatibility between hydrophilic PMPC brushes and hydrophobic tris(TMS). The anti-fouling characteristic of PMPC brushes, inferred from plasma protein adsorption, was subsequently varied by controlling the surface coverage ratio between PMPC brushes and tris(TMS).

Pyrolysis of waste electrical and electronic equipment: effect of antinomy trioxide on the pyrolysis of styrenic polymers.

This work has investigated the effect that antimony trioxide has on the pyrolysis of styrenic polymers and the effect that different types of brominated flame retardants used in plastics have on the composition of the pyrolysis products. Brominated high impact polystyrene (Br-HIPS) which contained either 5% or 0% antimony trioxide and either decabromodiphenyl oxide (DDO) or decabromodiphenyl ethane (DDE) was pyrolysed in a fixed bed reactor at 430 degrees C. Some experiments on the fixed bed reactor involved mixing the Br-HIPS with polystyrene. The gaseous products were analysed by GC-FID and GC-TCD and it was found that antimony trioxide caused an increase in the proportion of ethane and ethene and suppressed the proportion of butane and butene. When DDE was the flame retardant increased proportions of ethane and ethene were found in the pyrolysis gas compared to when DDO used. When polystyrene was mixed with the Br-HIPS it suppressed the trends observed in the gas composition during the pyrolysis of Br-HIPS. The pyrolysis oils were characterised using FT-IR, GC-MS, GC-FID, and GC-ECD. It was found that the plastic which did not contain antimony trioxide pyrolysed to form mainly toluene, ethylbenzene, styrene, cumene, and alpha-methylstyrene. The oils produced from the pyrolysis of the plastic that contained antimony trioxide did not contain any styrene or alpha-methylstyrene, but instead contained greater concentrations of ethylbenzene and cumene. The absence of styrene and alpha-methylstyrene from the pyrolysis oil occurred even when the Br-HIPS was mixed with polystyrene. GC-ECD analysis of the oils showed that the plastics which did not contain antimony trioxide pyrolysed to form (1-bromoethyl)benzene, which was totally absent from the pyrolysis oils when antimony trioxide was present in the plastic.