Photoinduced force microscopy as a novel method for the study of microbial nanostructures.

A detailed comparison of the capabilities of electron microscopy and nano-infrared (IR) microscopy for imaging microbial nanostructures has been carried out for the first time. The surface sensitivity, chemical specificity, and non-destructive nature of spectroscopic mapping is shown to offer significant advantages over transmission electron microscopy (TEM) for the study of biological samples. As well as yielding important topographical information, the distribution of amides, lipids, and carbohydrates across cross-sections of bacterial (Escherichia coli, Staphylococcus aureus) and fungal (Candida albicans) cells was demonstrated using PiFM. The unique information derived from this new mode of spectroscopic mapping of the surface chemistry and biology of microbial cell walls and membranes, may provide new insights into fungal/bacterial cell function as well as having potential use in determining mechanisms of antimicrobial resistance, especially those targeting the cell wall.

InP/ZnS quantum dot photoluminescence modulation via in situ H2S interface engineering.

InP quantum dots (QDs) are attracting significant interest as a potentially less toxic alternative to Cd-based QDs in many research areas. Although InP-based core/shell QDs with excellent photoluminescence properties have been reported so far, sophisticated interface treatment to eliminate defects is often necessary. Herein, using aminophosphine as a seeding source of phosphorus, we find that H2S can be efficiently generated from the reaction between a thiol and an alkylamine at high temperatures. Apart from general comprehension that H2S acts as a S precursor, it is revealed that with core etching by H2S, the interface between InP and ZnS can be reconstructed with S2- incorporation. Such a transition layer can reduce inherent defects at the interface, resulting in significant photoluminescence (PL) enhancement. Meanwhile, the size of the InP core could be further controlled by H2S etching, which offers a feasible process to obtain wide band gap InP-based QDs with blue emission.

The effect of dissolved chlorides on the photocatalytic degradation properties of titania in wastewater treatment.

We investigate the effect of chlorides on the photocatalytic degradation of phenol by titania polymorphs (anatase and rutile). We demonstrate how solubilised chlorides can affect the hydroxyl radical formation on both polymorphs with an overall effect on their photodegradative activity. Initially, the photocatalytic activity of anatase and rutile for phenol degradation is investigated in both standard water and brines. With anatase, a significant reduction of the phenol conversion rate is observed (from a pseudo-first-order rate constant k = 5.3 × 10-3 min-1 to k = 3.5 × 10-3 min-1). In contrast, the presence of solubilised chlorides results in enhancement of rutile activity under the same reaction conditions (from 2.3 × 10-3 min-1 to 4.8 × 10-3 min-1). Periodic DFT methods are extensively employed and we show that after the generation of charge separation in the modelled titania systems, adsorbed chlorides are the preferential site for partial hole localisation, although small energy differences are computed between partially localised hole densities over adsorbed chloride or hydroxyl. Moreover, chlorides can reduce or inhibit the ability of r-TiO2 (110) and a-TiO2 (101) systems to localise polarons in the slab structure. These results indicate that both mechanisms - hole scavenging and the inhibition of hole localisation - can be the origin of the effect of chlorides on photocatalytic activity of both titania polymorphs. These results provide fundamental insight into the photocatalytic properties of titania polymorphs and elucidate the effect of adsorbed anions over radical formation and oxidative decomposition of organic pollutants.

The interaction of CO with a copper(ii) chloride oxy-chlorination catalyst.

The interaction of CO with an attapulgite-supported, KCl modified CuCl2 catalyst has previously been examined using a combination of XANES, EXAFS and DFT calculations. Exposing the catalyst to CO at elevated temperatures leads to the formation of CO2 as the only identifiable product. However, phosgene production can be induced by a catalyst pre-treatment stage, where the supported CuCl2 sample is exposed to a diluted stream of dichlorine; subsequent CO exposure at ∼643 K then leads to phosgene production. This communication describes a series of FTIR based micro-reactor measurements, coupled with characterisation measurements utilising TEM, XRD and XPS to define the nature of the catalyst at different stages of the reaction coordinate. The CuCl2 catalyst is able to support Deacon activity , establishing this work with the possibility of utilising the oxy-chlorination of CO to produce phosgene. Continuous dosing of CO at elevated temperatures over the chlorine pre-dosed CuCl2 catalyst shows diminishing phosgene production as a function of time-on-stream, indicating surface chlorine supply to be rate-limiting under the reaction conditions studied. A pictorial reaction scheme is proposed to account for the surface chemistry observed.

The Role of Growth Directors in Controlling the Morphology of Hematite Nanorods.

The control of the growth of hematite nanoparticles from iron chloride solutions under hydrothermal conditions in the presence of two different structure promoters has been studied using a range of both structural and spectroscopic techniques including the first report of photo induced force microscopy (PiFM) to map the topographic distribution of the structure-directing agents on the developing nanoparticles. We show that the shape of the nanoparticles can be controlled using the concentration of phosphate ions up to a limit determined to be ~6 × 10-3 mol. Akaganéite (ß-FeOOH) is a major component of the nanoparticles formed in the absence of structure directors but only present in the very early stages (< 8 h) of particle growth when phosphate is present. The PiFM data suggest a correlation between the areas in which phosphate ions are adsorbed and areas where akaganéite persists on the surface. In contrast, goethite (α-FeOOH) is a directly observed precursor of the hematite nanorods when 1,2-diamino propane is present. The PiFM data shows goethite in the center of the developing particles consistent with a mechanism in which the iron hydroxide re-dissolves and precipitates at the nanorod ends as hematite.

The photocatalytic destruction of cinnamic acid and cinnamyl alcohol: Mechanism and the effect of aqueous ions.

Cinnamic acid was chosen as an exemplar molecule to study the effect of potential contaminants on the kinetics and mechanism of the photocatalytic destruction of hydrocarbons in aqueous solutions. We identify the principal intermediates in the photocatalytic reaction of the acid and corresponding alcohol, and propose a mechanism that explains the presence of these species. The impact of two likely contaminants of aqueous systems, sulfate and chloride ions were also studied. Whereas sulfate ions inhibit the degradation reaction at all concentrations, chloride ions, up to a concentration of 0.5 M, accelerate the removal of cinnamic acid from solution by a factor of 1.6. However, although cinnamic acid is removed, the pathway to complete oxidation is blocked by the chloride, with the acid being converted (in the presence of oxygen) into new products including acetophenone, 2-chloroacetophenone, 1-(2-chlorophenyl)ethenone and 1,2-dibenzoylethane. We speculate that the formation of these products involves chlorine radicals formed from the reaction of chloride ions with the photoinduced holes at the catalyst surface. Interestingly, we have shown that the 1-(2-chlorophenyl)ethenone and 1,2-dibenzoylethane products form from 2-chloroacetophenone when irradiated with 365 nm light in the absence of the catalyst. The formation of potentially dangerous side products in this reaction suggest that the practical implementation of the photocatalytic purification of contaminated water needs to considered very carefully if chlorides are likely to be present.

Rationalization of the X-ray photoelectron spectroscopy of aluminium phosphates synthesized from different precursors.

The aim of this paper is to clarify the assignments of X-ray photoelectron spectra of aluminium phosphate materials prepared from the reaction of phosphoric acid with three different aluminium precursors [Al(OH)3, Al(NO3)3 and AlCl3] at different annealing temperatures. The materials prepared have been studied by X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (XRD), infrared spectroscopy and high-resolution solid-state 31P NMR spectroscopy. A progressive polymerization from orthophosphate to metaphosphates is observed by XRD, ATR-FTIR and solid state 31P NMR, and on this basis the oxygen states observed in the XP spectra at 532.3 eV and 533.7 eV are assigned to P-O-Al and P-O-P environments, respectively. The presence of cyclic polyphosphates at the surface of the samples is also evident.

Rock-crushing derived hydrogen directly supports a methanogenic community: significance for the deep biosphere.

Microbial populations exist to great depths on Earth, but with apparently insufficient energy supply. Earthquake rock fracturing produces H2 from mechanochemical water splitting, however, microbial utilization of this widespread potential energy source has not been directly demonstrated. Here, we show experimentally that mechanochemically generated H2 from granite can be directly, long-term, utilized by a CH4 producing microbial community. This is consistent with CH4 formation in subsurface rock fracturing in the environment. Our results not only support water splitting H2 generation as a potential deep biosphere energy source, but as an oxidant must also be produced, they suggest that there is also a respiratory oxidant supply in the subsurface which is independent of photosynthesis. This may explain the widespread distribution of facultative aerobes in subsurface environments. A range of common rocks were shown to produce mechanochemical H2 , and hence, this process should be widespread in the subsurface, with the potential for considerable mineral fuelled CH4 production.

Structural behaviour of copper chloride catalysts during the chlorination of CO to phosgene.

The interaction of CO with an attapulgite-supported Cu(ii)Cl2 catalyst has been examined in a micro-reactor arrangement. CO exposure to the dried, as-received catalyst at elevated temperatures leads to the formation of CO2 as the only identifiable product. However, phosgene production can be induced by using a catalyst pre-treatment where the supported Cu(ii)Cl2 sample is exposed to a diluted stream of chlorine. Subsequent CO exposure at ∼370 °C then leads to phosgene production. In order to investigate the origins of this atypical set of reaction characteristics, a series of X-ray absorption experiments were performed that were supplemented by DFT calculations. XANES measurements establish that at the elevated temperatures connected with phosgene formation, the catalyst is comprised of Cu+ and a small amount of Cu2+. Moreover, the data show that unique to the chlorine pre-treated sample, CO exposure at elevated temperature results in a short-lived oxidation of the copper. On the basis of calculated CO adsorption energies, DFT calculations indicate that a mixed Cu+/Cu2+ catalyst is required to support CO chemisorption.

Production of Metal-Free Diamond Nanoparticles.

In this paper, the controlled production of high-quality metal-free diamond nanoparticles is demonstrated. Milling with tempered steel is shown to leave behind iron oxide contamination which is difficult to remove. Milling with SiN alleviates this issue but generates more nondiamond carbon. Thus, the choice of milling materials is critically determined by the acceptable contaminants in the ultimate application. The removal of metal impurities, present in all commercially available nanoparticles, will open new possibilities toward the production of customized diamond nanoparticles, covering the most demanding quantum applications.

A hybrid strain and thermal energy harvester based on an infra-red sensitive Er3+ modified poly(vinylidene fluoride) ferroelectret structure.

In this paper, a novel infra-red (IR) sensitive Er3+ modified poly(vinylidene fluoride) (PVDF) (Er-PVDF) film is developed for converting both mechanical and thermal energies into useful electrical power. The addition of Er3+ to PVDF is shown to improve piezoelectric properties due to the formation of a self-polarized ferroelectric ß-phase and the creation of an electret-like porous structure. In addition, we demonstrate that Er3+ acts to enhance heat transfer into the Er-PVDF film due to its excellent infrared absorbance, which, leads to rapid and large temperature fluctuations and improved pyroelectric energy transformation. We demonstrate the potential of this novel material for mechanical energy harvesting by creating a durable ferroelectret energy harvester/nanogenerator (FTNG). The high thermal stability of the ß-phase enables the FTNG to harvest large temperature fluctuations (ΔT ~ 24 K). Moreover, the superior mechanosensitivity, SM ~ 3.4 VPa-1 of the FTNG enables the design of a wearable self-powered health-care monitoring system by human-machine integration. The combination of rare-earth ion, Er3+ with the ferroelectricity of PVDF provides a new and robust approach for delivering smart materials and structures for self-powered wireless technologies, sensors and Internet of Things (IoT) devices.

Effect of slurry composition on the chemical mechanical polishing of thin diamond films.

Nanocrystalline diamond (NCD) thin films grown by chemical vapour deposition have an intrinsic surface roughness, which hinders the development and performance of the films' various applications. Traditional methods of diamond polishing are not effective on NCD thin films. Films either shatter due to the combination of wafer bow and high mechanical pressures or produce uneven surfaces, which has led to the adaptation of the chemical mechanical polishing (CMP) technique for NCD films. This process is poorly understood and in need of optimisation. To compare the effect of slurry composition and pH upon polishing rates, a series of NCD thin films have been polished for three hours using a Logitech Ltd. Tribo CMP System in conjunction with a polyester/polyurethane polishing cloth and six different slurries. The reduction in surface roughness was measured hourly using an atomic force microscope. The final surface chemistry was examined using X-ray photoelectron spectroscopy and a scanning electron microscope. It was found that of all the various properties of the slurries, including pH and composition, the particle size was the determining factor for the polishing rate. The smaller particles polishing at a greater rate than the larger ones.

Modifying the Interface Edge to Control the Electrical Transport Properties of Nanocontacts to Nanowires.

Selecting the electrical properties of nanomaterials is essential if their potential as manufacturable devices is to be reached. Here, we show that the addition or removal of native semiconductor material at the edge of a nanocontact can be used to determine the electrical transport properties of metal-nanowire interfaces. While the transport properties of as-grown Au nanocatalyst contacts to semiconductor nanowires are well-studied, there are few techniques that have been explored to modify the electrical behavior. In this work, we use an iterative analytical process that directly correlates multiprobe transport measurements with subsequent aberration-corrected scanning transmission electron microscopy to study the effects of chemical processes that create structural changes at the contact interface edge. A strong metal-support interaction that encapsulates the Au nanocontacts over time, adding ZnO material to the edge region, gives rise to ohmic transport behavior due to the enhanced quantum-mechanical tunneling path. Removal of the extraneous material at the Au-nanowire interface eliminates the edge-tunneling path, producing a range of transport behavior that is dependent on the final interface quality. These results demonstrate chemically driven processes that can be factored into nanowire-device design to select the final properties.

Characterization of the effects of n-butanol on the cell envelope of E. coli.

Biofuel alcohols have severe consequences on the microbial hosts used in their biosynthesis, which limits the productivity of the bioconversion. The cell envelope is one of the most strongly affected structures, in particular, as the external concentration of biofuels rises during biosynthesis. Damage to the cell envelope can have severe consequences, such as impairment of transport into and out of the cell; however, the nature of butanol-induced envelope damage has not been well characterized. In the present study, the effects of n-butanol on the cell envelope of Escherichia coli were investigated. Using enzyme and fluorescence-based assays, we observed that 1 % v/v n-butanol resulted in the release of lipopolysaccharides from the outer membrane of E. coli and caused 'leakiness' in both outer and inner membranes. Higher concentrations of n-butanol, within the range of 2-10 % (v/v), resulted in inner membrane protrusion through the peptidoglycan observed by characteristic blebs. The findings suggest that strategies for rational engineering of butanol-tolerant bacterial strains should take into account all components of the cell envelope.

Spectroscopic and atomic force studies of the functionalisation of carbon surfaces: new insights into the role of the surface topography and specific chemical states.

The utility of carbon materials in applications as diverse as drug delivery and photocatalysis is often undermined by the complexity of their surface chemistry; different sources of carbon give rise to a varied mixture of functional groups and hence different properties. Considerable efforts have been made to identify specific groups at these surfaces and elucidate the complex interactions that take place but even on materials such as graphene and carbon nanotubes there remains uncertainty about the nature of the components present and their role in the nucleation of other functional materials at the surface. The present study uses highly ordered pyrolytic graphite (HOPG) as a model on which the fundamental properties of specific functional groups and their interactions with deposited nanoparticles can be characterised. We have shown that treatment of HOPG surfaces with low concentrations of hydrochloric acid results in significant topographic changes to the surface and a low concentration of oxygen containing species. From selective derivatization and a comparison of their XP spectra, the latter can be unambiguously identified as surface hydroxyls. DFT calculations have shown that these groups are stable in close proximity to each other. Heating to 573 K leads to conversion of the hydroxyls to mixture of two states, one of which is identified as a ketone whilst the other is proposed to be an ether. Gold deposition on the surface from aqueous solutions of chloroauric acid is shown to be strongly influenced by the nature of the oxygen species present.