Nanoparticles used for medical applications commonly possess coatings or surface functionalities intended to provide specific behavior in vivo, for example, the use of PEG to provide stealth properties. Direct, quantitative measurement of the surface chemistry and composition of such systems in a hydrated environment has thus far not been demonstrated, yet such measurements are of great importance for the development of nanomedicine systems. Here we demonstrate the first use of cryo-XPS for the measurement of two PEG-functionalized nanomedicines: a polymeric drug delivery system and a lipid nanoparticle mRNA carrier. The observed differences between cryo-XPS and standard XPS measurements indicate the potential of cryo-XPS for providing quantitative measurements of such nanoparticle systems in hydrated conditions.
Nanomedicine , Nanoparticles , Polyethylene Glycols/chemistry , Drug Delivery Systems , Nanoparticles/chemistry , Polymers
The omnipresence of microplastics (MPs) across Earth's surface has raised concerns about their environmental impact and created an urgent need for methods to identify them in complex soil and sedimentary matrices. However, detecting MPs in the O horizons of soils is difficult because plastic polymers share many physical and chemical properties with natural soil organic matter (SOM). In this study, we assessed whether sodium hypochlorite (NaOCl), a reagent that can oxidize SOM and simultaneously preserve mineral constituents, can be used for MP analysis and characterization in soil environments. In addition, we scrutinized how factors such as MP size, polymer type, extraction methods, and soil matrix affect the recovery of microplastic particles. We used both hydrophobic and density-dependent separation methods to assess the effects of our oxidation treatment on the recovery of MP. We observed that NaOCl effectively removed SOM without greatly altering the surface properties of resistant MP polymers (polypropylene, polylactic acid, low-density polyethylene, and polyethylene terephthalate), which were characterized using scanning electron microscopy and Fourier-transform infrared spectroscopy after SOM removal. The NaOCl treatment caused some chlorination and formation of additional C-OH bonds on polymer surfaces, which likely contributed to the reduced efficiency of the hydrophobic-based (oil) extraction. We conclude that NaOCl treatment can improve detection of MPs in SOM-rich soil and that recovery of MPs from soils is influenced by MP size, polymer type, extraction method, and soil type, which makes it challenging to develop a universal analytical method.
Microplastics , Water Pollutants, Chemical , Environmental Monitoring , Oxidants , Plastics , Sodium Hypochlorite , Soil
Interaction between microorganisms and their surroundings are generally mediated via the cell wall or cell envelope. An understanding of the overall chemical composition of these surface layers may give clues on how these interactions occur and suggest mechanisms to manipulate them. This knowledge is key, for instance, in research aiming to reduce colonization of medical devices and device-related infections from different types of microorganisms. In this context, X-ray photoelectron spectroscopy (XPS) is a powerful technique as its analysis depth below 10 nm enables studies of the outermost surface structures of microorganism. Of specific interest for the study of biological systems is cryogenic XPS (cryo-XPS). This technique allows studies of intact fast-frozen hydrated samples without the need for pre-treatment procedures that may cause the cell structure to collapse or change due to the loss of water. Previously, cryo-XPS has been applied to study bacterial and algal surfaces with respect to their composition of lipids, polysaccharides and peptide (protein and/or peptidoglycan). This contribution focuses onto two other groups of microorganisms with widely different architecture and modes of life, namely fungi and viruses. It evaluates to what extent existing models for data treatment of XPS spectra can be applied to understand the chemical composition of their very different surface layers. XPS data from model organisms as well as reference substances representing specific building blocks of their surface were collected and are presented. These results aims to guide future analysis of the surface chemical composition of biological systems.
Birnessite is a layered MnO2 mineral capable of intercalating nanometric water films in its bulk. With its variable distributions of Mn oxidation states (MnIV, MnIII, and MnII), cationic vacancies, and interlayer cationic populations, birnessite plays key roles in catalysis, energy storage solutions, and environmental (geo)chemistry. We here report the molecular controls driving the nanoscale intercalation of water in potassium-exchanged birnessite nanoparticles. From microgravimetry, vibrational spectroscopy, and X-ray diffraction, we find that birnessite intercalates no more than one monolayer of water per interlayer when exposed to water vapor at 25 °C, even near the dew point. Molecular dynamics showed that a single monolayer is an energetically favorable hydration state that consists of 1.33 water molecules per unit cell. This monolayer is stabilized by concerted potassium-water and direct water-birnessite interactions, and involves negligible water-water interactions. Using our composite adsorption-condensation-intercalation model, we predicted humidity-dependent water loadings in terms of water intercalated in the internal and adsorbed at external basal faces, the proportions of which vary with particle size. The model also accounts for additional populations condensed on and between particles. By describing the nanoscale hydration of birnessite, our work secures a path for understanding the water-driven catalytic chemistry that this important layered manganese oxide mineral can host in natural and technological settings.
Grafting of electrodes with diazonium salts using cyclic voltammetry (CV) is a well-established procedure for surface modification. However, little is known about the effect of the concentration of the diazonium salt on the number of layers grafted on the electrode surface. In this work, the impact of concentration on the grafting of 4-carboxybenzenediazonium (4-CBD) onto a glassy carbon electrode (GCE) is elucidated. The number of layers grafted on the GCE was linearly dependent on the concentration of 4-CBD and varied between 0.9 and 4.3 when the concentration was varied between 0.050 and 0.30 mmol/L at 0.10 V.s-1. Characterization of modified glassy carbon surface with X-ray photoelectron spectroscopy (XPS) confirmed the grafting of carboxyphenyl layer on the surface. Grafting with 0.15 mmol/L 4-CBD (1 CV cycle) did not form a detectable amount of carboxyphenyl (CP) moieties at the surface, while a single scan with higher concentration (2.5 mmol/L) or multiple scans (22 cycles) gave detectable signals, indicating formation of multilayers. We also demonstrate the possibility of removing the thin layer grafted on a glassy carbon electrode by applying high oxidation potential +1.40 V.
Borates/chemistry , Carbon/chemistry , Electrochemistry/methods , Electrodes , Oxidation-Reduction
Herein, we report on the use a biohybrid catalyst consisting of palladium nanoparticles immobilized on cross-linked enzyme aggregates of lipaseâ B of Candida antarctica (CalB CLEA) for the dynamic kinetic resolution (DKR) of benzylic amines. A set of amines were demonstrated to undergo an efficient DKR and the recyclability of the catalysts was studied. Extensive efforts to further elucidate the structure of the catalyst are presented.
Earth-abundant cobalt-doped hematite thin-film electrocatalysts were explored for acidic water oxidation. The strategically doped hematite produced a stable geometric current density of 10 mA cm-2 for up to 50 h at pH 0.3, as a result of Co-enhanced intrinsic catalytic activity and charge transport properties across the film matrix.
A highly selective and efficient oxidative carbocyclization/borylation of enallenols catalyzed by palladium immobilized on amino-functionalized siliceous mesocellular foam (Pd-AmP-MCF) was developed for diastereoselective cyclobutenol synthesis. The heterogeneous palladium catalyst can be recovered and recycled without any observed loss of activity or selectivity. The high diastereoselectivity of the reaction is proposed to originate from a directing effect of the enallenol hydroxyl group. Optically pure cyclobutenol synthesis was achieved by the heterogeneous strategy by using chiral enallenol obtained from kinetic resolution.
Electrolyte ion binding at mineral surfaces is central to the generation of surface charge and key to electric double-layer formation. X-ray photoelectron spectroscopy of fast-frozen (-170 °C) mineral wet pastes provides a means to study weakly bound electrolyte ions at the mineral/water interface. In this study, we build upon a series of articles devoted to ion binding at hematite (α-Fe2O3) particle surfaces to resolve the nature of sodium halide ion binding. Measurements on micron-sized hematite particles terminated by the charged and amphoteric (012) and the relatively uncharged (001) faces point to the formation of salt loadings of similar composition to those of cryosalts of NaCl, NaBr, NaI, and NaF. These coatings could be likened to those of the better-known hydrohalite (NaCl·2H2O) phase, one that typically forms under concentrated (â«0.1 M) aqueous solutions of NaCl under freezing conditions. As we have previously shown that these reaction products do not occur in nanosized hematite particles, our work points to the involvement of the basal (001) face and/or the juxtaposition of these faces in packed tabular microparticles of hematite (1-3 µm in width) in stabilizing these cryosalts. One possible formation pathway involves first-layer Na+ and Cl- ions serving as an anchoring layer for a topotactic-like growth of amorphous to low-crystalline salt hydrates at the (001) face. Thus, by contrasting reaction products of four sodium halides at surfaces of tabular microparticles of hematite, this work revealed the formation of cryosalt-like solids. The formation of such solids may have especially important ramifications to ice nucleation mechanisms in the atmosphere, as well as in saline permafrosts on Earth and on planet Mars where salt-laden mineral particles prevail.
To exploit the full potential of hematite (α-Fe2O3) as an efficient photoanode for water oxidation, the redox processes occurring at the Fe2O3/electrolyte interface need to be studied in greater detail. Ex situ doping is an excellent technique to introduce dopants onto the photoanode surface and to modify the photoanode/electrolyte interface. In this context, we selected antimony (Sb5+) as the ex situ dopant because it is an effective electron donor and reduces recombination effects and concurrently utilize the possibility to tuning the surface charge and wettability. In the presence of Sb5+ states in Sb-doped Fe2O3 photoanodes, as confirmed by X-ray photoelectron spectroscopy, we observed a 10-fold increase in carrier concentration (1.1 × 1020 vs 1.3 × 1019 cm-3) and decreased photoanode/electrolyte charge transfer resistance (â¼990 vs â¼3700 Ω). Furthermore, a broad range of surface characterization techniques such as Fourier-transform infrared spectroscopy, ζ-potential, and contact angle measurements reveal that changes in the surface hydroxyl groups following the ex situ doping also have an effect on the water splitting capability. Theoretical calculations suggest that Sb5+ can activate multiple Fe3+ ions simultaneously, in addition to increasing the surface charge and enhancing the electron/hole transport properties. To a greater extent, the Sb5+- surface-doped determines the interfacial properties of electrochemical charge transfer, leading to an efficient water oxidation mechanism.
We introduce a new method of evaluating the structure of electric double layer (EDL) at the native solid/liquid interface using cryogenic X-ray photoelectron spectroscopy technique. This method is based on evaluating the atomic concentration ratio of counterions and co-ions of supporting electrolyte at the close-to-in situ state surface of colloid particles by the cryo-XPS and comparing it with analogous ratio predicted by EDL models. For silica colloids in aqueous KCl solutions at pH 6 to 8 it has been found that the latter ratio is higher than unity, as expected for the negatively charged surface of silica, but does not correspond with the prediction of the basic Gouy-Chapman EDL model for the ideal interface. However, it agrees with that deduced from experiments on electrolytic coagulation kinetics of analogous silica colloids by applying a simple EDL model of swellable ion-permeable (Donnanian) polyelectrolyte gel layer. It turns out that the traditional Stern layer-based concept of EDL at solid/liquid interfaces is not justified for metal oxides at least in KCl solutions.
This article describes an attempt to develop a sensor based on multi-frequency immittance spectroscopy for the determination of methotrexate (MTX) in blood serum using gold electrodes modified with antibodies. The attachment of antibodies was monitored with electrochemical immittance spectroscopy (EIS) and X-ray photoelectron spectroscopy (XPS). The EIS measurements of MTX resulted in a data matrix of size 39 × 55. The data were analysed using multivariate data analysis and showed a concentration dependence and time dependence that could be separated. This allowed the calculation of a multivariate calibration model. The model showed good linear behavior on a logarithmic scale offering a detection limit of 5 × 10-12 mol L-1.
Biosensing Techniques , Dielectric Spectroscopy , Electrochemical Techniques , Methotrexate/blood , Electrodes , Gold , Humans , Serum/chemistry
Herein we report a 3D heterostructure comprising a hierarchical macroporous carbon foam that incorporates mesoporous carbon nanotubes decorated with cobalt oxide nanoparticles as an unique and highly efficient electrode material for the oxygen evolution reaction (OER) in electrocatalytic water splitting. The best performing electrode material showed high stability after 10 h, at constant potential of 1.7 V vs. RHE (reversible hydrogen electrode) in a 0.1 M KOH solution and high electrocatalytic activity in OER with low overpotential (0.38 V vs RHE at 10 mA cm-2). The excellent electrocatalytic performance of the electrode is rationalized by the overall 3D macroporous structure and with the firmly integrated CNTs directly grown on the foam, resulting in a large specific surface area, good electrical conductivity, as well as an efficient electrolyte transport into the whole electrode matrix concurrent with an ability to quickly dispose oxygen bubbles into the electrolyte. The eminent properties of the three-dimensional structured carbon matrix, which can be synthesized through a simple, scalable and cost effective pyrolysis process show that it has potential to be implemented in large-scale water electrolysis systems.
This chapter describes a method for measuring the average surface chemical composition with respect to lipids, polysaccharides, and peptides (protein + peptidoglycan) for the outer part of the bacterial cell wall. Bacterial cultures grown over night are washed with a buffer or saline at controlled pH. The analysis is done on fast-frozen bacterial cell pellets obtained after centrifugation, and the analysis requires access to X-ray photoelectron spectroscopy instrumentation that can perform analyses at cryogenic temperatures (for example using liquid nitrogen). The method can be used to monitor changes in the cell wall composition following environmental stimuli or genetic mutations. The data obtained originate from the outermost part of the cell wall. Thus, it is expected that for gram-negative bacteria only the outer membrane and part of the periplasmic peptidoglycan layer is probed during analysis, and for gram-positive bacteria only the top nanometers of the peptidoglycan layer of the cell wall is monitored.
Cell Wall/chemistry , Lipids/analysis , Peptides/analysis , Polysaccharides, Bacterial/analysis , Bacterial Proteins/analysis , Cell Membrane/chemistry , Gram-Negative Bacteria/chemistry , Gram-Negative Bacteria/growth & development , Gram-Positive Bacteria/chemistry , Gram-Positive Bacteria/growth & development , Photoelectron Spectroscopy
This study uncovers bifluoride-type (difluorohydrogenate(i); [HF2](-)) species formed at mineral/water interfaces. Bifluoride forms at [triple bond, length as m-dash]Al-F surface sites resulting from the partial fluoridation of gibbsite (γ-Al(OH3)) and bayerite (α-Al(OH3)) particles exposed to aqueous solutions of 50 mM NaF. Fluoride removal from these solutions is proton-promoted and results in a strongly self-buffered suspensions at circumneutral pH, proceeds at a F : H consumption ratio of 2 : 1, and with recorded losses of up to 17 mM fluoride (58 F nm(-2)). These loadings exceed crystallographic site densities by a factor of 3-4, yet the reactions have no resolvable impact on particle size, shape and mineralogy. X-ray photoelectron spectroscopy (XPS) of frozen (-155 °C) wet mineral pastes revealed coexisting surface F(-) and HF(0) species. Electron energy loss features pointed to multilayer distribution of these species at the mineral/water interface. XPS also uncovered a distinct form of Na(+) involved in binding fluoride-bearing species. XPS and solid state magic angle spinning (19)F nuclear magnetic resonance measurements showed that these fluoride species were highly comparable to a sodium-bifluoride (NaHF2) reference. First layer surface species are represented as [triple bond, length as m-dash]Al-F-H-F-Al[triple bond, length as m-dash] and [triple bond, length as m-dash]Al-F-Na-F-Al[triple bond, length as m-dash], and may form multi-layered species into the mineral/water interface. These results consequently point to a potentially overlooked inorganic fluorine species in a technologically relevant mineral/water interfacial systems.
Adsorption of antibiotics at mineral surfaces has been extensively studied over the past 20 years, yet much remains to be learned on their interfacial properties and transformation mechanisms. In this study, interactions of Ciprofloxacin (CIP), a fluoroquinolone antibiotic with two sets of synthetic nanosized hematite particles, with relatively smooth (H10, 10-20 nm in diameter) and roughened (H80, 80-90 nm in diameter) surfaces, were studied by means of liquid chromatography (LC), mass spectrometry (MS), and spectroscopy (vibration and X-ray photoelectron). Attenuated Total Reflectance Fourier Transform Infrared (ATR-FTIR) spectroscopy provides evidence for inner-sphere bidentate complex formation of CIP at hematite surfaces in 0.01 M NaCl, irrespective of pH and particle size. ATR-FTIR spectroscopy also revealed that the sorbed mother CIP molecule decayed to other surface species over a period of at least 65 h. This was supported by the detection of three daughter products in the aqueous phase by LC/MS. The appearance of NH3(+) groups during the course of these experiments, revealed by cryogenic XPS, provides further evidence that CIP oxidation proceeds through an opening of piperazine ring via N-dealkylation. Additional in vacuo FTIR experiments under temperature-programmed desorption also showed that oxidation of sorbed byproducts were effectively degraded beyond 450 °C, a result denoting considerably strong (inter)molecular bonds of both mother and daughter products. This work also showed that rougher, possibly multidomainic particles (H80) generated slower rates of CIP decomposition but occurring through more complex schemes than at smoother particle surfaces (H10). This work thus uncovered key aspects of the binding of an important antibiotic at iron oxide surfaces, and therefore provided additional constraints to our growing understanding of the fate of emerging contaminants in the environment.
Ciprofloxacin/chemistry , Ferric Compounds/chemistry , Hydrogen-Ion Concentration , Kinetics , Oxidation-Reduction , Photoelectron Spectroscopy , Spectroscopy, Fourier Transform Infrared , Surface Properties , Temperature
The sluggish kinetics of the oxygen reduction reaction at the cathode side of proton exchange membrane fuel cells is one major technical challenge for realizing sustainable solutions for the transportation sector. Finding efficient yet cheap electrocatalysts to speed up this reaction therefore motivates researchers all over the world. Here we demonstrate an efficient synthesis of palladium-tungsten bimetallic nanoparticles supported on ordered mesoporous carbon. Despite a very low percentage of noble metal (palladium:tungsten=1:8), the hybrid catalyst material exhibits a performance equal to commercial 60% platinum/Vulcan for the oxygen reduction process. The high catalytic efficiency is explained by the formation of small palladium islands embedded at the surface of the palladium-tungsten bimetallic nanoparticles, generating catalytic hotspots. The palladium islands are ~1 nm in diameter, and contain 10-20 palladium atoms that are segregated at the surface. Our results may provide insight into the formation, stabilization and performance of bimetallic nanoparticles for catalytic reactions.
Polysulfides are often referred to as key reactants in the sulfur cycle, especially during the interaction of ferric (hydr)oxides and sulfide, forming ferrous-sulphide minerals. Despite their potential relevance, the extent of polysulfide formation and its relevance for product formation pathways remains enigmatic. We applied cryogenic X-ray Photoelectron Spectroscopy and wet chemical analysis to study sulfur oxidation products during the reaction of goethite and lepidocrocite with aqueous sulfide at different initial Fe/S molar ratios under anoxic conditions at neutral pH. The higher reactivity of lepidocrocite leads to faster and higher electron turnover compared to goethite. We were able to demonstrate for the first time the occurrence of surface-associated polysulfides being the main oxidation products in the presence of both minerals, with a predominance of disulfide (S2(2-)(surf)), and elemental sulfur. Concentrations of aqueous polysulfide species were negligible (<1%). With prior sulfide fixation by zinc acetate, the surface-associated polysulfides could be precipitated as zerovalent sulfur (S°), which was extracted by methanol thereafter. Of the generated S°, 20-34% were associated with S2(2-)(surf). Varying the Fe/S ratio revealed that surface polysulfide formation only becomes dominant when the remaining aqueous sulfide concentration is low (<0.03 mmol L(-1)). We hypothesize these novel surface sulfur species, particularly surface disulfide, to act as pyrite precursors. We further propose that these species play an overlooked role in the sulfur cycle.
Ferric Compounds/chemistry , Sulfides/chemistry , Oxidation-Reduction , Photoelectron Spectroscopy , Sulfides/analysis
Studies on noble-metal-decorated carbon nanostructures are reported almost on a daily basis, but detailed studies on the nanoscale interactions for well-defined systems are very rare. Here we report a study of reduced graphene oxide (rGOx) homogeneously decorated with palladium (Pd) nanoclusters with well-defined shape and size (2.3 ± 0.3 nm). The rGOx was modified with benzyl mercaptan (BnSH) to improve the interaction with Pd clusters, and N,N-dimethylformamide was used as solvent and capping agent during the decoration process. The resulting Pd nanoparticles anchored to the rGOx-surface exhibit high crystallinity and are fully consistent with six-shell cuboctahedral and icosahedral clusters containing ~600 Pd atoms, where 45% of these are located at the surface. According to X-ray photoelectron spectroscopy analysis, the Pd clusters exhibit an oxidized surface forming a PdO(x) shell. Given the well-defined experimental system, as verified by electron microscopy data and theoretical simulations, we performed ab initio simulations using 10 functionalized graphenes (with vacancies or pyridine, amine, hydroxyl, carboxyl, or epoxy groups) to understand the adsorption process of BnSH, their further role in the Pd cluster formation, and the electronic properties of the graphene-nanoparticle hybrid system. Both the experimental and theoretical results suggest that Pd clusters interact with functionalized graphene by a sulfur bridge while the remaining Pd surface is oxidized. Our study is of significant importance for all work related to anchoring of nanoparticles on nanocarbon-based supports, which are used in a variety of applications.
Bacteria play an important role in the biogeochemical cycling of metals in the environment. Consequently, there is an interest to understand how the bacterial surfaces interact with metals in solution and how this affects the bacterial surface. In this work we have used a surface-sensitive analysis technique, cryogenic X-ray photoelectron spectroscopy (cryo-XPS), to monitor the surface of Bacillus subtilis cells as a function of pH and Zn(2+) content in saline solution. The objective of the study was twofold: (1) to investigate the agreement between two data treatment methods for XPS, as well as investigate to what extent sample pretreatment may influence XPS data of bacterial samples, and (2) to characterize how the surface chemistry of bacterial cells is influenced by different external conditions. (1) It was found that the two data treatment methods gave rise to comparable results. However, identical samples analyzed fast-frozen or dry exhibited larger differences in surface chemistry, indicating that sample pretreatment can to large extents influence the obtained surface composition of bacterial samples. (2) The bacterial cell wall (in fast-frozen samples) undergoes dramatic compositional changes with pH and with Zn(2+) exposure. The compositional changes are interpreted as an adaptive metal resistance response changing the biochemical composition of the bacterial cell wall. These results have implications for how adsorption processes at the surface of bacterial cells are analyzed, understood, modeled, and predicted.
Bacillus subtilis/drug effects , Bacillus subtilis/metabolism , Cell Wall/drug effects , Cell Wall/metabolism , Photoelectron Spectroscopy/methods , Zinc/pharmacology , Hydrogen-Ion Concentration
