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The biopersistence of fiber materials is one of the cornerstones in estimating potential risk to human health upon inhalation. To connect epidemiological and in vivo investigations with in vitro studies, reliable and robust methods of fiber biopersistence determination and understanding of fiber dissolution mechanism are required. We investigated dissolution properties of oil treated stone wool fibers with and without sugar-based binder (SBB) at 37 °C in the liquids representing macrophages intracellular conditions (pH 4.5). Conditions varied from batch to flow of different rates. Fiber morphology and surface chemistry changes caused by dissolution were monitored with scanning electron microscopy and time-of-flight secondary ion mass spectrometry mapping. Stone wool fiber dissolution rate depends on liquid composition (presence of ligands, such as citrate), pH, reaction products transport and fibers wetting properties. The dissolution rate decreases when: 1) citrate is consumed by the reaction with the released Al cations; 2) the pH increases during a reaction in poorly buffered solutions; 3) the dissolution products are accumulated; 4) fibers are not fully wetted with the fluid. Presence of SBB has no influence on dissolution rate if fiber material was wetted prior to dissolution experiment to avoid poorly wetted fiber agglomerates formation in the synthetic lung fluids.

Electrochemical CO2 reduction to valuable chemicals represents a greenand sustainable approach to close the anthropogenic carbon cycle, but hasbeen impeded by low efficiency and high cost of electrocatalysts. Here, acost-effective hybrid catalyst consisting of hemin (chloroprotoporphyrin IXiron(III)), a product recovered from bovine blood, adsorbed onto commercialVulcan carbon is reported. Upon heat treatment, this material shows significantlyimproved activity and selectivity for CO2 reduction in water whileexhibiting good stability for more than 10 h. The heat treatment leads toconsecutive removal of the axial chlorine atom and decomposition of the ironporphyrin ring, restructuring to form atomic Fe sites. The optimized hybridcatalyst obtained at 900 °C shows near-unity selectivity for reduction of CO2to CO at a small overpotential of 310 mV. The insight into transformation ofadsorbed Fe complexes into single Fe atoms upon heat treatment providesguidance for development of single atom catalysts.

Interactions between graphene oxide (GO) and organic molecules play a role in processes such as environmental remediation and water treatment. However, little is known about underlying molecular level processes with the presence of ions. In this study, we utilized atomic force microscopy (AFM) in chemical force mapping (CFM) mode to directly probe their adhesion interactions. AFM tips were functionalised to serve as models for nonpolar and polar organic molecules, i.e. with alkyl, –CH3, and carboxyl, –COO(H). For experiments with –COO(H) tips, adhesion between GO and tips decreased in the order: Ba2+ > Ca2+ > Mg2+ > Na+, whereas for the –CH3 tips, ion dependent adhesion was relatively low but followed the same: Ba2+ > Ca2+ > Mg2+ ≈ Na+. Calculations with Derjaguin–Landau–Verwey–Overbeek (DLVO) theory and the Schulze–Hardy rule could not account for the observations. We propose that ion bridging plays a definitive role in adhesion between –COO(H) tips and the GO surface. This is consistent with proposed models with density functional theory (DFT) calculations. Adhesion of –CH3 tips is a response to the hydrophilic interactions and the ion dependent part is suggested to arise from ion bridging between slightly negative charged –CH3 tips and the GO surface. High pH had a notable influence on the adhesion of the –COO(H) tip but a negligible effect on the –CH3 tip. These results offer important insights into interactions between solutions and mineral surfaces with adsorbed organic molecules.

Simultaneous retention of SMM behaviour and of optical activity is demonstrated upon surface deposition for a chiral SMM., The synthesis and characterization of a chiral, enneanuclear Mn(iii)-based, Single-Molecule Magnet, [Mn9O4(Me-sao)6(L)3(MeO)3(MeOH)3]Cl (1; Me-saoH2 = methylsalicylaldoxime, HL = lipoic acid) is reported. Compound 1 crystallizes in the orthorhombic P212121 space group and consists of a metallic skeleton describing a defect super-tetrahedron missing one vertex. The chirality of the [MnIII9] core originates from the directional bridging of the Me-sao2– ligands via the –N–O– oximate moieties, which define a clockwise (1ΔΔ) or counter-clockwise (1ΛΛ) rotation in both the upper [MnIII3] and lower [MnIII6] subunits. Structural integrity and retention of chirality upon dissolution and upon deposition on (a) gold nanoparticles, 1@AuNPs, (b) transparent Au(111) surfaces, 1ΛΛ@t-Au(111); 1ΔΔ@t-Au(111), and (c) epitaxial Au(111) on mica surfaces, 1@e-Au(111), was confirmed by CD and IR spectroscopies, mass spectrometry, TEM, XPS, XAS, and AFM. Magnetic susceptibility and magnetization measurements demonstrate the simultaneous retention of SMM behaviour and optical activity, from the solid state, via dissolution, to the surface deposited species.

The Au-C linkage has been demonstrated as a robust interface for coupling thin organic films on Au surfaces. However, the nature of the Au-C interaction remains elusive up to now. Surface-enhanced Raman spectroscopy was previously used to assign a band at 412 cm(-1) as a covalent sigma Au-C bond for films generated by spontaneous reduction of the 4-nitrobenzenediazonium salt on Au nanoparticles. However, this assignment is disputed based on our isotopic shift study. We now provide direct evidence for covalent Au-C bonds on the surface of Au nanoparticles using C-13 crosspolarization/magic angle spinning solid-state NMR spectroscopy combined with isotope substitution. A C-13 NMR shift at 165 ppm was identified as an aromatic carbon linked to the gold surface, while the shift at 148 ppm was attributed to C-C junctions in the arylated organic film. This demonstration of the covalent sigma Au-C bond fills the gap in metal-C bonds for organic films on surfaces, and it has great practical and theoretical significance in understanding and designing a molecular junction based on the Au-C bond.

The design of selective and efficient catalysts for electrochemical CO2 reduction is highly desirable yet still challenging, in particular, if the aim is to make them binder-free and self-standing. Here, we report a new and straightforward strategy to incorporate Ni single atoms into a commercially available carbon paper to prepare a self-standing electrode. This is accomplished by consecutive acid activation, adsorption of Ni2+ ions, and pyrolysis steps. Structural characterizations and calculations based on density functional theory consistently suggest that the Ni single atoms are coordinated with three N and one S atoms on the carbon paper. When used for CO2 electroreduction, the electrode exhibits an optimal selectivity (91%), activity (3.4 mA cm-2), and stability (at least 14 h) for CO production in water at an overpotential of 660 mV. This report may inspire the design and incorporation of single atoms of various metal types into carbon papers, or other kinds of carbon substrates, for a wide range of electrocatalytic processes. This journal is

Cu is in the spotlight as it represents the only metal capable of catalyzing CO2 reduction to multicarbon products. However, its catalytic performance is determined collectively by a number of parameters including its composition and structure, electrolyte, and cell configuration. It remains a challenge to disentangle and understand the individual effect of these parameters. In this work, we study the effect of the electrode-electrolyte interface on CO2 reduction in water by coating CuO electrodes with polymers of varying hydrophilicities/phobicities. Hydrophilic polymers such as poly(vinyl alcohol) and poly(vinylpyrrolidone) exert negligible influence, while hydrophobic polymers such as poly(vinylidene fluoride) and polyethylene significantly enhance the activity, selectivity, and stability of CuO-derived electrodes toward C2H4 production. From ex situ characterizations, electrolysis in deuterated water, and molecular dynamics simulations, we propose that the improved catalytic performance triggered by hydrophobic polymers originates from restricted water diffusion and a higher local pH near the electrode surface. These observations shed light on interfacial manipulation for promoted CO2-to-C2H4 conversion.

The stability of phenol-urea-formaldehyde (PUF) binder and 3-aminopropylsilane (APS) on composite silicate materials (fibers and wafers) was studied with surface sensitive techniques (X-ray photoelectron spectroscopy (XPS) and streaming potential) through a wide range of humidity and temperature and ab initio modelling complemented the results. Behavior was compared for wettability properties, determined by vapor adsorption and contact angle analysis. APS and PUF, deposited on the silicate surfaces, decrease surface energy and wettability but water adsorption remains high, facilitating hydrolytic decomposition of the composite material. Deposited APS is unstable at T>50 degrees C and 75% RH, while PUF is less sensitive to high humidity and temperature. Molecular dynamics confirmed APS sensitivity to humidity. Water adsorption and surface energy decrease, and material stability increases when a hydrophobization agent is applied to APS/PUF treated surfaces. The direct correlation between wettability and stability of PUF/APS/fiber composites can contribute in designing new materials with controlled hydrophobic properties. (C) 2020 Elsevier Ltd. All rights reserved.

Lignin is currently an underutilized part of biomass, thus, further research into lignin could benefit both scientific and commercial endeavors. The present study investigated the potential of kraft lignin as a support material for the removal of hydrogen sulfide (H2S) from gaseous streams, such as biogas. The removal of H2S was enabled by copper ions that were previously adsorbed on kraft lignin. Copper adsorption was based on two different strategies: either directly on lignin particles or by precipitating lignin from a solution in the presence of copper. The H2S concentration after the adsorption column was studied using proton-transfer-reaction mass spectrometry, while the mechanisms involved in the H2S adsorption were studied with X-ray photoelectron spectroscopy. It was determined that elemental sulfur was obtained during the H2S adsorption in the presence of kraft lignin and the differences relative to the adsorption on porous silica as a control are discussed. For kraft lignin, only a relatively low removal capacity of 2 mg of H2S per gram was identified, but certain possibilities to increase the removal capacity are discussed.

The production of novel composite materials, assembled using biomimetic polymers known as peptoids (N-substituted glycines) to nucleate CaCO3, can open new pathways for advanced material design. However, a better understanding of the heterogeneous CaCO3 nucleation process is a necessary first step. We determined the thermodynamic and kinetic parameters for calcite nucleation on self-assembled monolayers (SAMs) of nanosheet-forming peptoid polymers and simpler, alkanethiol analogues. We used nucleation rate studies to determine the net interfacial free energy (γnet) for the peptoid–calcite interface and for SAMs terminated with carboxyl headgroups, amine headgroups, or a mix of the two. We compared the results with γnet determined from dynamic force spectroscopy (DFS) and from density functional theory (DFT), using COSMO-RS simulations. Calcite nucleation has a lower thermodynamic barrier on the peptoid surface than on carboxyl and amine SAMs. From the relationship between nucleation rate (J0) and saturation state, we found that under low-saturation conditions, i.e., We have combined nucleation studies, dynamic force spectroscopy, and density functional theory and determined the thermodynamic and kinetic parameters for calcite nucleation on self-assembled monolayers (SAMs) of nanosheet-forming peptoid polymers and simpler, alkanethiol analogues. Our results show insight into biopolymeric influence on nucleation and growth of a mineral phase during biomineralization processes and are directly applicable to nacre mimicry.

The properties and behavior of the interface between mineral surfaces, adsorbed organic compounds, and water are important for oil recovery. Low-salinity (LS) water flooding releases more oil from sandstone reservoirs than conventional flooding with seawater or formation water. However, the role of strongly adsorbed organic material, as an anchor for oil molecules, is not yet completely understood. Here, we mimic reservoir pore surfaces using graphene oxide sheets deposited on flat silicon wafers. The LS response was quantified using atomic force microscopy (AFM) in chemical force mapping mode to directly measure the adhesion force. AFM tips were functionalized to serve as models for hydrophobic and polar oil molecules, i.e., with alkyl, −CH3, and carboxyl, −COO(H). Adhesion force, measured with −CH3 tips, was 18% lower in LS (∼1500 ppm) than high-salinity (HS, ∼35 600 ppm) solutions, while for −COO(H) tips, adhesion force was 13% lower in LS than HS solutions. The Dejarguin–Landau–Verwey–Overbeek theory ...

Flooding sandstone oil reservoirs with low salinity water can lead to a significant increase in oil recovery, a phenomenon called “the low salinity effect”. Although there are many factors that contribute to this response, the surface tension on the pore walls is an important one. Sandstone is composed predominantly of quartz with some clay, but feldspar grains are often also present. While the wettability of quartz and clay surfaces has been thoroughly investigated, little is known about the adhesion properties of feldspar. We explored the interaction of model oil compounds, molecules that terminate with carboxyl, −COO(H), and alkyl, −CH3, with freshly cleaved, museum quality perthitic microcline, KxNa(1–x)AlSi3O8, a K-feldspar. Microcline is a member of the orthoclase family, a type of feldspar that weathers more slowly than the plagioclase series, and thus is more likely to be preserved in well sorted sandstone. Adhesion forces, measured with the chemical force mapping (CFM) mode of atomic force micros...

3-Aminopropylsilane (APS) coupling agent is widely used in industrial, biomaterial, and medical applications to improve adhesion of polymers to inorganic materials. However, during exposure to elevated humidity and temperature, the deposited APS layers can decompose, leading to reduction in coupling efficiency, thus decreasing the product quality and the mechanical strength of the polymer-inorganic material interface. Therefore, a better understanding of the chemical state and stability of APS on inorganic surfaces is needed. In this work, we investigated APS adhesion on silica wafers and compared its properties with those on complex silicate surfaces such as those used by industry (mineral fibers and fiber melt wafers). The APS was deposited from aqueous and organic (toluene) solutions and studied with surface sensitive techniques, including X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), streaming potential, contact angle, and spectroscopic ellipsometry. APS configuration on a model silica surface at a range of coverages was simulated using density functional theory (DFT). We also studied the stability of adsorbed APS during aging at high humidity and elevated temperature. Our results demonstrated that APS layer formation depends on the choice of solvent and substrate used for deposition. On silica surfaces in toluene, APS formed unstable multilayers, while from aqueous solutions, thinner and more stable APS layers were produced. The chemical composition and substrate roughness influence the amount of deposited APS. More APS was deposited and its layers were more stable on fiber melt than on silica wafers. The changes in the amount of adsorbed APS can be successfully monitored by streaming potential. These results will aid in improving industrial- and laboratory-scale APS deposition methods and increasing adhesion and stability, thus increasing the quality and effectiveness of materials where APS is used as a coupling agent.

The wettability of mineral surfaces controls a range of phenomena in natural and industrial processes. In reservoirs, rock wettability determines the effectiveness of oil production; thus, modification of mineral surface properties can lead to enhanced oil recovery. Recent work reports that potential determining ions in seawater, Mg2+, Ca2+, and SO42–, are responsible for altering the wettability of calcite surfaces. In favorable conditions, e.g., elevated temperature, calcium at the calcite surface can be replaced by magnesium, making organic molecules bind more weakly and water molecules bind more strongly, rendering the surface more hydrophilic. We used atomic force microscopy in chemical force mapping mode to probe the adhesion forces between a hydrophobic CH3-terminated AFM tip and a freshly cleaved calcite {10.4} surface to investigate wettability change in the presence of Mg2+ and SO42– at 75 and 80 °C. We made submicrometer scale maps of adhesion force and contact angle and demonstrated that the a...

The unambiguous determination of the chemical functionality over graphene oxide (GO) is important to unleash its potential applications. However, the mapping of oxygen functionalities distribution remains to be unequivocally determined because of highly inhomogeneous non-stoichiometric structures and ultra-thin layers of GO. In this study, we report an experimental observation of the spatial distribution of oxygen functional groups on monolayer and multilayer GO using AFM-IR, atomic force microscopy coupled with infrared spectroscopy. Overcoming conventional IR diffraction limit for several micrometers, the novel AFM-IR reaches high spatial resolution ∼20 nm and could detect IR absorption on ∼1 nm thickness of monolayer GO. With nanoscale chemical mapping, the distribution of different oxygen functional groups is distinguished with AFM-IR over the GO surface. It allows us to observe that these oxygen functional groups prefer to sit on the fold areas, in discrete domains and on the edges of GO, which gave more insights into its chemical nature. The determination of the position of functional groups through precise imaging contributes to our understanding of GO structure-properties relations and paves the way for targeted tethering of polymers, biomaterials, and other nanostructures.

The removal of bromide (Br − ) and iodide (I − ) from source waters mitigates the formation of brominated and iodinated disinfection by-products (DBPs), which are more toxic than their chlorinated analogues. In this study, we report on our recently developed environmental-friendly method for the preparation of novel silver chloride/superfine activated carbon composite (AgCl-SPAC) to rapidly and selectively remove Br − and I − from surface waters. The material characteristics were tracked, before and after treatment, using scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), X-ray diffraction (XRD), and X-ray photoelectron spectra (XPS) spectroscopies. The results showed very fast removal kinetics of Br − and I − by AgCl-SPAC with equilibrium times at 150 s and − concentrations up to 400 mg/L and exhibited high removal efficiencies for I − (i.e., >90% at all tested conditions) and Br − (i.e, >80% at Cl − = 0.5–200 mg/L, and 60–75% at extreme Cl − conditions = 300–400 mg/L). Unlike previous Ag-based composites, AgCl-SPAC performance was not affected by elevated concentrations of two types of natural organic matter (2–16 mg-NOM/L). The superior performance was further confirmed in four different surface waters and one groundwater. After the removal of Br − and I − from all waters by AgCl-SPAC, the subsequent DBPs formation (trihalomethanes, haloacetic acids, and haloacetonitriles), total organic halogens (TOX), bromine substitution factor (BSF), and calculated cytotoxicity under the uniform formation conditions (UFC) decreased significantly. Overall, this novel composite represents a promising alternative approach, to be integrated continuously or seasonally, for controlling the formation of brominated and/or iodinated DBPs at water treatment plants.

Understanding the adsorption behavior of nitrogen heterocyclic compounds (NHCs) on soil minerals underlies more effective design of wastewater treatment and soil/groundwater remediation. We investigated adsorption of quinoline, a representative NHC, on quartz sand (using Berea sandstone as a model), at 3 < pH < 9, in low (0.05 M) and high (0.7 M) ionic strength solutions where NaCl was the background electrolyte. Minor clay (kaolinite) in the sandstone contributed significantly to quinoline uptake. Adsorption peaked at pH∼6. It decreased from 2 equivalent monolayers at low ionic strength to a monolayer at NaCl activity approaching that of seawater. A triple layer surface complexation model fits the data well, where quartz and kaolinite contributed sites for three types of quinoline (Q) complexes: 1) innersphere ≡SiOHQ; 2) outersphere ≡SiO-QH+ and 3) innersphere ≡AlOHQ2. Aluminol kaolinite sites promote multilayer quinoline adsorption, whereas only monolayers form on silanol sites. Site density calculations and molecular dynamics (MD) confirmed that quinoline adsorbs upright, on edge, and multilayer adsorption follows formation of the initial monolayer. Our results confirm the effectiveness of sand(stones) and clays for removing NHCs from waste and groundwaters.

Considerable interest in calcite crystallization has prompted many studies on organic molecule adsorption. However, each study has explored only a few compounds, using different methods and conditions, so it is difficult to combine the results into a general model that describes the fundamental mechanisms. Our goal was to develop a comprehensive adsorption model from the behavior of a range of organic compounds by exploring how common functional groups interact with calcite and the effects of various side groups and hydrogen on adsorption. We used density functional theory, with semiempirical dispersion corrections (DFT-D2), to determine adsorption energy on calcite {10.4} for nonpolar (benzene, ethane, and carbon dioxide) and oxygen containing polar molecules (water, methanol, ethanol, phenol, formic acid, acetic acid, propanoic acid, benzoic acid, formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, dimethyl ether, acetone, and furan). From the adsorption energies, within the transition state theo...

Sulfur and nitrogen are two common constituents of natural and synthetic organic molecules, especially in systems where organisms play a role. There is evidence in the literature that nitrogen and sulfur containing functional groups have an influence on adsorption of organic molecules to calcite surfaces. The purpose of this work was to investigate the interaction of these functional groups with CaCO3 and to explore how adsorption is affected by various side groups and the H atom. First, we used density functional theory with semiempirical dispersion corrections (DFT-D2) to determine the energy of adsorption on the dominant calcite face, {10.4} for molecules containing nitrogen (ammonia, methylamine, ethylamine, aniline, hydrogen cyanide, acetonitrile, propionitrile, benzonitrile, dimethylamine, pyrrole, trimethylamine, and pyridine) and sulfur (hydrogen sulfide, methanethiol, ethanethiol, thiophenol, dimethyl sulfide, and thiophene). Second, based on the determined adsorption energies, we predicted desor...

Graphene oxide (GO) is an interesting material that has the potential for a wide range of applications. Critical for these applications are the type of oxygen bond and its spatial distribution on the individual GO sheets. This distribution is not yet well understood. Few techniques offer a resolution high enough to unambiguously identify oxygen configuration. We used a new, label free spectroscopic technique to map oxygen bonding on GO, with spatial resolution of nanometres and high chemical specificity. AFM-IR, atomic force microscopy coupled with infrared spectroscopy, overcomes conventional IR diffraction limits, producing IR spectra from specific points as well as chemical maps that are coupled to topography. We have directly observed oxygen bonding preferentially on areas where graphene is folded, in discrete domains and on edges of GO. From these observations, we propose an updated structural model for GO, with C O on its edge and plane, which confirms parts of earlier proposed models. The results have interesting implications. Determining atomic position and configuration from precise imaging offers the possibility to link nanoscale structure and composition with material function, paving the way for targeted tethering of ions, polymers and biomaterials.

Phenol-urea-formaldehyde (PUF) resin is one of the most important thermosetting polymers. It is widely used in many industrial and construction applications as an organic coating and adhesive. For example, in production of mineral wool for insulation, PUF is used together with the coupling agent (3-aminopropylsilane, APS) and serves as a binder for attaching mineral fibers to each other and to create the necessary mechanical integrity and shape of the final product. However, during ageing under high humidity (95%) and temperature (70 °C), hydrolysis can degrade PUF, decreasing product quality. A better understanding of the chemical processes caused by hydrolysis would promote development of more stable PUF binders. We investigated the composition and stability changes during ageing of cured PUF powder binder and mineral wool fibers where PUF binds the fibers together. We aged the samples in hot water (80 °C) or in a controlled climate chamber (70 °C; 91% RH) and analyzed them using X-ray photoelectron spectroscopy (XPS), element analysis and thermogravimetric (TG) analysis. We investigated the composition of species released from PUF during hydrolysis by electrospray ionization (ESI) of the aqueous solutions. The results show that the extent of PUF curing and the presence of APS as the coupling agent have an important impact on its stability. XPS revealed that poorly cured PUF contains a high fraction of –NH–CH2–O–CH2–NH– bonds which are easily hydrolyzed, while longer curing results mostly in more stable methylene bridges, –NH–CH2–NH–. We also observed evidence for urea –NH–CO– bond decomposition by ESI analysis. Mineral wool fiber ageing studies showed that PUF rearranges on the fiber surface and detaches from it, together with the APS coupling agent. This improved understanding of the effects of ageing provides clues for designing a more robust binder, leading to increased quality and stability of mineral wool insulation.

A versatile method based on electrografting of aryldiazonium salts was used to introduce covalently attached initiators for atom transfer radical polymerization (ATRP) on glassy carbon surfaces. Polymer brushes of ferrocenylmethyl methacrylate were prepared from the surface-attached initiators, and these films were thoroughly analyzed using various techniques, including X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy (IRRAS), ellipsometry, and electrochemistry. Of particular interest was the electrochemical characterization of the electron transfer through the diazonium-based initiator layer to the redox centers in the polymer brush films. It was found that the apparent rate constant of electron transfer decreases exponentially with the dry-state thickness of this layer. To investigate the electron transfer in the brushes themselves, scanning electrochemical microscopy (SECM) was applied, thereby allowing the effect from the initiator layer to be excluded. The unusual transition feature of the approach curves recorded suggests that an initial fast charge transfer to the outermost-situated ferrocenyl groups is followed by a slower electron transport involving the neighboring redox units.

Reaction mechanisms in the Al(CH3)3–D2O–Si2(NHEt)6–D2O ALD process for AlxSiyOz were studied in situ with a quartz crystal microbalance (QCM) and a quadrupole mass spectrometer (QMS) at 200 °C. Two...

This study elucidates the influence of the atom trans- fer radical polymerization initiator structure, monolayer versus disordered multilayer, on the growth kinetics and the structural transition of poly(methyl methacrylate) (PMMA) brush layers. The multilayer initiator film, prepared by acylation of the electro- grafted 2-phenylethanol layer using 2-bromoisobutyryl bromide, consists of � 4.6 times more tert-butyl bromide groups compared to monolayer initiator prepared by self assembly technique. The results demonstrate the formation of precursor complex between Cu I catalyst and the bromine initiator as a prerequisite step before the onset of polymerization. Furthermore, the PMMA brushes formed by the polymerization from the multilayered initiator layer at 50 � C are 20-fold thicker compared to the polymerization at 25 � C due to the swelling of the multilayered initiator film. In con- trast, the thickness of the PMMA layer on the monolayer initiator is less affected by the polymerization temperature. By varying the initiator density on the surface, the solvent content in the PMMA layer is shown to vary from 15% to 94%, resulting in the transition from concentrated over semidiluted to diluted brushes. V C 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 50: 4465- 4475, 2012

The reaction between a nucleophilic 4-(2-aminoethyl)phenyl-tethered glassy carbon surface and various para-substituted aryl isocyanates [ONC-PhX; X = NO(2), COPh, Cl, H, and NMe(2)] has been studied in toluene. It is demonstrated that the nucleophilic addition reaction is relatively fast occurring within two hours while providing an efficient and versatile route for derivatizing alkylamine-functionalized surfaces. An often overlooked issue in surface reactions is the possibility for competing physisorption processes. In such cases, the solution-based reactants become adsorbed to the surface or embedded in the grafted layer rather than chemically bonded to the surface. It is shown that for two of the aryl isocyanates (X = NO(2) and COPh) this physical adhesion can be so strong that even prolonged ultrasonic treatment cannot remove the adsorbant. However, a single potential excursion is capable of desorbing most of the physisorbed layers. The isocyanate-based method is also compared with the well-known approaches involving diazonium salts for assembling similar chemical systems directly. It is concluded that the method can be used advantageously not only in cases, where such approaches should fall short, but also if the goal is to achieve better control of the positioning of, e.g., redox active molecules in a well-defined layer with the ultimate goal of obtaining distinct electrochemical responses.

We describe for the first time the electro-oxidative synthesis and passivating properties of surface films of poly(allylamine) and copolymers of allylamine and diallylamine. Cyclic voltammetry and impedance spectra show that the films exhibit high charge-transfer resistance and that the addition of diallylamine causes improvements in the compactness and stability toward swelling of the films when compared to both allylamine and diallyamine, leading to coatings with high charge-transfer resistance up to 70 MΩ. We also show that removing oxygen before the polymerization further improves the films’ passivating properties.

An electrochemical approach is introduced for the versatile carboxylation of multi-layered graphene in 0.1 M Bu4NBF4/MeCN. First, the graphene substrate (i.e., graphene chemically vapor-deposited on Ni) is negatively charged at -1.9 V versus Ag/AgI in a degassed solution to allow for intercalation of Bu4N(+) and, thereby, separation of the individual graphene sheets. In the next step, the strongly activated and nucleophilic graphene is allowed to react with added carbon dioxide in an addition reaction, introducing carboxylate groups stabilized by Bu4N(+) already present. This procedure may be carried out repetitively to further enhance the carboxylation degree under controlled conditions. Encouragingly, the same degree of control is even attainable, if the intercalation and carboxylation is carried out simultaneously in a one-step procedure, consisting of simply electrolyzing in a CO2-saturated solution at the graphene electrode for a given time. The same functionalization degree is obtained for all multi-layered regions, independent of the number of graphene sheets, which is due to the fact that the entire graphene structure is opened in response to the intercalation of Bu4N(+). Hence, this electrochemical method offers a versatile procedure to make all graphene sheets in a multi-layered but expanded structure accessible for functionalization. On a more general level, this approach will provide a versatile way of forming new hybrid materials based on intimate bond coupling to graphene via carboxylate groups.

Electrografting using aryldiazonium salts provides a fast and efficient technique to functionalize commercially available 3-5 layered graphene (vapour-deposited) on nickel. In this study, Raman spectroscopy is used to quantify the grafting efficiency of cyclic voltammetry which is one of the most versatile, yet simple, electrochemical techniques available. To a large extent the number of defects/substituents introduced to the basal plane of high-quality graphene by this procedure can be controlled through the sweeping conditions employed. After extended electrografting the defect density reaches a saturation level ( ∼ 10(13) cm(-2)) which is independent of the quality of the graphene expressed through its initial content of defects. However, it is reached within fewer voltammetric cycles for low-quality graphene. Based on these results it is suggested that the grafting occurs (a) directly at defect sites for, in particular, low-quality graphene, (b) directly at the basal plane for, in particular, high-quality graphene, and/or (c) at already grafted molecules to give a mushroom-like film growth for all films. Moreover, it is shown that a tertiary alkyl bromide can be introduced at a given surface density to serve as radical initiator for surface-initiated atom transfer radical polymerization (SI-ATRP). Brushes of poly(methyl methacrylate) are grown from these substrates, and the relationship between polymer thickness and sweeping conditions is studied.

This work demonstrates the application of carbohydrate based methacrylate polymer brush, poly(2-lactobionamidoethyl methacrylate), for the purpose of cell adhesion studies. The first part of the work illustrates the effects of the structure of the aminosilane based ATRP initiator layer on the polymerization kinetics of 2-lactobionamidoethyl methacrylate) (LAMA) monomer on thermally oxidized silicon wafer. Both monolayer and multilayered aminosilane precursor layers have been prepared followed by reaction with 2-bromoisobutyrylbromide to form the ATRP initiator layer. It is inferred from the kinetic studies that the rate of termination is low on a multilayered initiator layer compared to a disordered monolayer structure. However both initiator types results in similar graft densities. Furthermore, it is shown that thick comb-like poly(LAMA) brushes can be constructed by initiating a second ATRP process on a previously formed poly(LAMA) brushes. The morphology of human hepatocellular carcinoma cancer cells (HepG2) on the comb-like poly(LAMA) brush layer has been studied. The fluorescent images of the HepG2 cells on the glycopolymer brush surface display distinct protrusions that extend outside of the cell periphery. On the other hand the cells on bare glass substrate display spheroid morphology. Further analysis using ToF-SIMS imaging shows that the HepG2 cells on glycopolymer surfaces is enriched with protein fragment along the cell periphery which is absent in the case of cells on bare glass substrate. It is suggested that the interaction of the galactose units of the polymer brush with the asialoglycoprotein receptor (ASGPR) of HepG2 cells has resulted in the protein enrichment along the cell periphery.

cited By 24; International audience; Thick conductive layers containing anthraquinone moieties are covalently immobilized on gold using redox grafting of the diazonium salt of anthraquinone (i.e., 9,10-dioxo-9,10-dihydroanthracene-1-diazonium tetrafluoroborate). This grafting procedure is based on using consecutive voltammetric sweeping and through this exploiting fast electron transfer reactions that are mediated by the anthraquinone redox moieties in the film. The fast film growth, which is followed by infrared reflection absorption spectroscopy, atomic force microscopy, X-ray photoelectron spectroscopy, ellipsometry, and coverage calculation, results in a mushroom-like structure. In addition to varying the number of sweeps, layer thickness control can easily be exerted through appropriate choice of the switching potential and sweep rate. It is shown that the grafting of the diazonium salt is essentially a diffusion-controlled process but also that desorption of physisorbed material during the sweeping process is essentially for avoiding blocking of the film due to clogging of the electrolyte channels in the film. In general, sweep rates higher than 0.5 V s -1 are required if thick, porous, and conducting films should be formed. © 2011 American Chemical Society.

Immobilization of submonolayers to 4-5 multilayers of organic molecules on carbon surfaces can be performed by in situ generation of aryl radicals from aryltriazenes. The central idea consists of oxidatively forming an electrogenerated acid of N,N'-diphenylhydrazine to convert the aryltriazene to the corresponding diazonium salt in the diffusion layer of the electrode. In a second step, the diazonium salt is reduced at the same electrode to give a surface of covalently attached aryl groups. In this manner, various moieties tethered to the aryl groups can be immobilized on the surface. Here a ferrocenyl group was introduced as redox marker, the electrochemical signal of which is extraordinarily well-defined. This behavior is independent of film thickness, the latter being easily controlled by the number of repetitive cycles performed. It is also demonstrated that the new approach is suitable for patterning of surfaces using scanning electrochemical microscopy.

Chromium surfaces can be electrografted with organic surfacefilms using 4-nitro- or 4-fluorobenzenediazonium salts, despitethe fact that the surfaces are covered with a protective chromiumoxide layer

Phenylethanethiolate monolayer-protected Au38 and Au140 nanoclusters were modified by ligand place exchange with a series of thiolated peptides. The peptides were homooligomers based on the alpha-aminoisobutyiric acid unit. The effects of changing the peptide concentration and the peptide length in the capping monolayer were studied by differential pulse voltammetry. The results showed that the redox behavior of the nanoparticles can be affected very significantly by such modifications. For example, the first oxidation peak of Au38, a cluster displaying molecule-like behavior, could be shifted positively by as much as 0.7-0.8 V. Detectable redox shifts were noted even when one single oriented peptide was in the Au140 monolayer. These effects were attributed to the molecular dipole moments of the peptide ligands.

Graphite-like thin films with excellent electrode properties were obtained by pyrolysis of nanometer thick electrografted layers of polyphenylene and polyanthracene layers on silicon substrates in a forming gas atmosphere. The pyrolyzed grafted films, characterized by using different surface analytical techniques such as ellipsometry, cyclic voltammetry, Raman spectroscopy, X-ray photo-electron spectroscopy, atomic force microscopy, and transmission electron microscopy, consist of graphite-like layers of ∼6 nm crystallite thickness with electrochemical properties that are similar to those of pyrolyzed photoresist films. Hence, pyrolysis of covalently bonded organic layers is an alternative approach to obtain very thin conducting carbon films strongly attached to a substrate. Furthermore, this technique can be applied to substrates of any geometrical structure, in contrast to spin coating techniques. It is suggested that thin graphite-like films on silicon produced in this manner could serve as substrate for spectroelectrochemical investigations of surface reactions by attenuated total reflectance experiment or in the production of optically transparent electrodes.