Modification of Polysulfide Surfaces with Low-Power Lasers.

The modification of polymer surfaces using laser light is important for many applications in the nano-, bio- and chemical sciences. Such capabilities have supported advances in biomedical devices, electronics, information storage, microfluidics, and other applications. In most cases, these modifications require high power lasers that are expensive and require specialized equipment and facilities to minimize risk of hazardous radiation. Additionally, polymer systems that can be easily modified by lasers are often complex and costly to prepare. In this report, these challenges are addressed with the discovery of low-cost sulfur copolymers that can be rapidly modified with lasers emitting low-power infrared and visible light. The featured copolymers are made from elemental sulfur and either cyclopentadiene or dicyclopentadiene. Using a suite of lasers with discreet wavelengths (532, 638 and 786 nm) and powers, a variety of surface modifications could be made on the polymers such as controlled swelling or etching via ablation. The facile synthesis and laser modification of these polymer systems were exploited in applications such as direct laser lithography and erasable information storage.

Microplastics in urban freshwater streams in Adelaide, Australia: A source of plastic pollution in the Gulf St Vincent.

The pollution of marine environments from plastic waste is anticipated to increase with current increases in plastic production. Reciprocally, escalating research efforts provide an improved understanding, monitoring, awareness, and mitigation of plastic contamination. Freshwater streams are recognised as one of the main contributors of microplastic pollution in marine environments. Presented here is the first investigation on the abundance of microplastic contamination (>20 µm and <5 mm) in freshwater streams in Adelaide, Australia. Composite samples were obtained from the sub-surface waters of eight freshwater streams (Magazine Wetland, Torrens River, Brownhill Creek, Sturt River, Field River, Christie Creek, Onkaparinga River and Pedler Creek), just before their connection to the Gulf St Vincent. Microplastics were found in all samples and microplastic abundance was 6.4 ± 5.5 particles.L-1 across all streams, with significant variations. Microplastic abundances found in the freshwater streams of Adelaide were comparatively higher than those found in areas of similar urbanisation, likely due to the varying methodologies used across studies. This work provides evidence, for the first time, of the prevalence of microplastic contamination in the sub-surface waters of eight freshwater streams in metropolitan Adelaide. These findings reinforce the need for long-term and on-going monitoring of freshwater streams for plastic contamination. Furthermore, spatial and temporal monitoring will allow for the identification in changes to the abundances of microplastics discharging from these sources into the Gulf St Vincent and observe if abundances increase or decrease with any future targeted waste management efforts.

Correlated Product Distributions in the Photodissociation of à State NO-CH4 and NO-N2 van der Waals Complexes.

This paper reports correlated product distributions for dissociation of the van der Waals complexes NO-CH4 and NO-N2 on their à state surfaces, providing detailed data sets against which calculations can be benchmarked. NO-CH4 dissociation strongly favors small changes in the CH4 angular momentum, with ΔJ = 0 and 1 providing the bulk of the products. Conversely, the associated NO products show little constraint in terms of the rotational angular momentum transfer, with the full range of energetically accessible angular momentum states populated, although the distributions show minima. The lack of angular momentum transfer to methane accompanied by broad, structured, angular momentum transfer to NO gives the NO-CH4 dissociation some qualitative similarities to NO-Rg complex dissociation. In contrast, for NO-N2, the cluster of highest probability products corresponds to high N2 angular momentum and low NO angular momentum, with a sharp drop in the probability for populating the highest energetically accessible J states. For both the NO and N2 products, there appears to be a constraint limiting angular momentum transfer at the highest energetically accessible rotational states. Both complexes show product distributions that include a component attributed to excitation from warm complexes, which provides insight into their internal energies. Interestingly, for NO-N2, the 44,475 cm-1 photolysis translational energy release distribution for N = 8 extends to energies beyond those accessible from the highest bound X̃ states. This indicates either that there are long-lived (>100 µs) states above the X̃ state binding energy or that there is another mechanism that also contributes to this distribution.

Can Aggregate-Associated Organisms Influence the Fouling in a SWRO Desalination Plant?

This pilot study investigates the formation of aggregates within a desalination plant, before and after pre-treatment, as well as their potential impact on fouling. The objective is to provide an understanding of the biofouling potential of the feed water within a seawater reverse osmosis (SWRO) desalination plant, due to the limited removal of fouling precursors. The 16S and 18S rRNA was extracted from the water samples, and the aggregates and sequenced. Pre-treatment systems, within the plant remove < 5 µm precursors and organisms; however, smaller size particles progress through the plant, allowing for the formation of aggregates. These become hot spots for microbes, due to their nutrient gradients, facilitating the formation of niche environments, supporting the proliferation of those organisms. Aggregate-associated organisms are consistent with those identified on fouled SWRO membranes. This study examines, for the first time, the factors supporting the formation of aggregates within a desalination system, as well as their microbial communities and biofouling potential.

Strong Torsion-Vibration Interaction in N-Methylpyrrole Observed by Far-Infrared Spectroscopy.

An interaction between methyl torsion and the low-lying out-of-plane methyl wag vibration has been observed in toluene, p-fluorotoluene, and m-fluorotoluene, contravening the traditional assumption used when analyzing spectra that methyl torsion can be treated independently of the small-amplitude vibrations. When a methyl group is attached to a planar frame, out-of-plane methyl wag vibrations always occur, and hence this type of interaction between methyl torsion and vibration is potentially extensive. To probe whether this coupling occurs beyond toluene and its derivatives, we have studied the far-infrared absorption band for the out-of-plane methyl wagging mode in N-methylpyrrole. The torsional sequence structure reveals a particularly strong torsion-vibration interaction. Spectral simulations yield a torsion-vibration coupling matrix element of 34.0 cm-1, over twice the value for toluene. The large torsion-vibration coupling constant implies that there is a significant tilting of the methyl group out of plane. Quantum chemistry calculations reveal a much larger out-of-plane methyl tilt angle in N-methylpyrrole compared to toluene, qualitatively consistent with this expectation. This is the first nontoluene derivative for which this type of torsion-vibration interaction has been reported and shows that the effect extends beyond toluenes. When present, this interaction links small-amplitude vibrations to the methyl torsion, providing a mechanism to bring the increased density of states into play and accelerate the rate of intramolecular vibrational energy redistribution.

Simulating the Feasibility of Using Liquid Micro-Jets for Determining Electron-Liquid Scattering Cross-Sections.

The extraction of electron-liquid phase cross-sections (surface and bulk) is proposed through the measurement of (differential) energy loss spectra for electrons scattered from a liquid micro-jet. The signature physical elements of the scattering processes on the energy loss spectra are highlighted using a Monte Carlo simulation technique, originally developed for simulating electron transport in liquids. Machine learning techniques are applied to the simulated electron energy loss spectra, to invert the data and extract the cross-sections. The extraction of the elastic cross-section for neon was determined within 9% accuracy over the energy range 1-100 eV. The extension toward the simultaneous determination of elastic and ionisation cross-sections resulted in a decrease in accuracy, now to within 18% accuracy for elastic scattering and 1% for ionisation. Additional methods are explored to enhance the accuracy of the simultaneous extraction of liquid phase cross-sections.

Torsion-vibration interactions determined from (far) infrared spectra.

Observations of the torsional and low-lying vibrational-torsional states of toluene, p-fluorotoluene, and m-fluorotoluene using the technique of two dimensional laser induced fluorescence (2D-LIF) have revealed interactions between the methyl torsion and low frequency out-of-plane methyl wagging vibration. These interactions can change the values of constants extracted from the analysis of rotational spectra, which usually assume that the large amplitude torsional motion can be treated independent of the small amplitude vibrations. Since out-of-plane methyl wagging modes will be present whenever a methyl group is attached to a planar frame, this type of torsion-vibration interaction is potentially widespread; it is thus important to establish the extent and strength of this type of interaction. 2D-LIF is limited to molecules that fluoresce from excited electronic states, and to explore interactions between torsion and methyl wagging vibrations in a wide range of molecules necessitates developing alternative experimental approaches. Infrared absorption spectroscopy is one such approach. It is shown that for the low torsional barrier case, the torsional sequence bands accompanying the out-of-plane methyl wagging transition provide a sensitive probe of the interaction. As an illustration, the far infrared absorption spectrum of toluene in the region of the M20 band (∼205 cm-1) is presented and analyzed. The torsional sequence structure provides insight into the higher torsional states (up to m = 7) in the ground vibrational state and M20. An analysis of these bands enables the torsion-vibration coupling and torsional constants to be extracted. A general method to analyze such spectra is presented.

High shear in situ exfoliation of 2D gallium oxide sheets from centrifugally derived thin films of liquid gallium.

A diversity of two-dimensional nanomaterials has recently emerged with recent attention turning to the post-transition metal elements, in particular material derived from liquid metals and eutectic melts below 330 °C where processing is more flexible and in the temperature regime suitable for industry. This has been explored for liquid gallium using an angled vortex fluidic device (VFD) to fabricate ultrathin gallium oxide (Ga2O3) sheets under continuous flow conditions. We have established the nanosheets to form highly insulating material and have electrocatalytic activity for hydrogen evolution, with a Tafel slope of 39 mV dec-1 revealing promoting effects of the surface oxidation (passivation layer).

Xylitol pentanitrate - Its characterization and analysis.

Xylitol is a polyhydric alcohol that may be nitrated to form an explosive (xylitol pentanitrate or XPN). Consequently, forensic and first response personnel may encounter XPN in post-blast residues or as a bulk material. Despite this, key analytical data for XPN that may be used in first response or forensic operations to aid its detection are not yet available in the literature. The present article provides infrared spectrometry, Raman spectrometry, nuclear magnetic resonance spectrometry, chromatography and mass spectrometry data in order to address this knowledge gap.

Reactive Compression Molding Post-Inverse Vulcanization: A Method to Assemble, Recycle, and Repurpose Sulfur Polymers and Composites.

Inverse vulcanization provides dynamic and responsive materials made from elemental sulfur and unsaturated cross-linkers. These polymers have been used in a variety of applications such as energy storage, infrared optics, repairable materials, environmental remediation, and precision fertilizers. In spite of these advances, there is a need for methods to recycle and reprocess these polymers. In this study, polymers prepared by inverse vulcanization are shown to undergo reactive compression molding. In this process, the reactive interfaces of sulfur polymers are brought into contact by mechanical compression. Upon heating these molds at relatively low temperatures (≈100 °C), chemical bonding occurs at the polymer interfaces by S-S metathesis. This method of processing is distinct from previous studies on inverse vulcanization because the polymers examined in this study do not form a liquid phase when heated. Neither compression nor heating alone was sufficient to mold these polymers into new architectures, so this is a new concept in the manipulation of sulfur polymers. Additionally, high-level ab initio calculations revealed that the weakest S-S bond in organic polysulfides decreases linearly in strength from a sulfur rank of 2 to 4, but then remains constant at about 100 kJ mol-1 for higher sulfur rank. This is critical information in engineering these polymers for S-S metathesis. Guided by this insight, polymer repair, recycling, and repurposing into new composites was demonstrated.

A strong interaction between torsion and vibration in S0 and S1m-fluorotoluene.

We report results of a two dimensional laser induced fluorescence study of torsional states, low frequency vibrations, and combinations of torsion with low frequency vibration in m-fluorotoluene up to 560 cm-1 in S0 and 350 cm-1 in S1. Evidence is presented for interactions between torsion and low frequency vibrations in both S0 and S1, demonstrating that the coupling of torsion and vibration observed previously in toluene and p-fluorotoluene extends to a molecule with a threefold torsional barrier. This barrier is low in S0 (20 cm-1) and modest in S1 (116 cm-1). The methyl torsion-vibration interaction is much larger for the mode involving out-of-plane wagging of the methyl group with respect to the planar frame compared with the analogous out-of-plane fluorine atom motion. Methyl group out-of-plane modes were found to be most important for torsion-vibration interactions in toluene and p-fluorotoluene, and the evidence is accumulating that this motion is fundamental in torsion-vibration interactions. Fits of the experimental band positions yield torsion-vibration coupling constants, torsional potential terms (V3 and V6), and rotational constants (F) for the methyl torsion in S0 and S1. The inclusion of torsion-vibration coupling primarily affects V6 and F: |V6| is reduced and F increased, as was seen previously for the G12 molecules, toluene and p-fluorotoluene. The torsional barrier height does not appear to influence the magnitude of the torsion-vibration interaction: the coupling constants for the out-of-plane CH3 wag mode are almost the same in S0 and S1 (15.5 cm-1 and 14.0 cm-1, respectively).

Sulfur polymer composites as controlled-release fertilisers.

Sulfur polymer composites were prepared by the reaction of canola oil and elemental sulfur in the presence of the NPK fertiliser components ammonium sulfate, calcium hydrogen phosphate, and potassium chloride. These composites released nutrients in a controlled fashion, resulting in less wasted fertiliser and better health for potted tomato plants when compared to free NPK.

Pervasive interactions between methyl torsion and low frequency vibrations in S0 and S1p-fluorotoluene.

We report two dimensional laser induced fluorescence spectral images exploring the lower torsion-vibration manifolds in S0 (E < 560 cm-1) and S1 (E < 420 cm-1) p-fluorotoluene. Analysis of the images reveals strong torsion-vibration interactions and provides an extensive set of torsion-vibration state energies in both electronic states (estimated uncertainty ±0.2 cm-1), which are fit to determine key constants including barrier heights, torsional constants, and torsion-vibration interaction constants. The dominant interactions in both electronic states are between methyl torsion (internal rotation) and the lowest frequency out-of-plane modes, D20 and D19, both of which involve a methyl wagging motion. This is the second aromatic (following toluene) for which a significant interaction between torsion and methyl out-of-plane wagging vibrations has been quantified. Given the generic nature of this motion in substituted toluenes and similar molecules, this mechanism for torsion-vibration coupling may be common in these types of molecules. The inclusion of torsion-vibration coupling affects key molecular constants such as barrier heights and torsional (and rotational) constants, and the possibility of such an interaction should thus be considered in spectral analyses when determining parameters in these types of molecules. p-Fluorotoluene is the first molecule in which the role of methyl torsion in promoting intramolecular vibrational energy redistribution (IVR) was established and the observed torsion-vibration coupling provides one conduit for the state mixing that is a precursor to IVR, as originally proposed by Moss et al. [J. Chem. Phys. 86, 51 (1987)].

Laying Waste to Mercury: Inexpensive Sorbents Made from Sulfur and Recycled Cooking Oils.

Mercury pollution threatens the environment and human health across the globe. This neurotoxic substance is encountered in artisanal gold mining, coal combustion, oil and gas refining, waste incineration, chloralkali plant operation, metallurgy, and areas of agriculture in which mercury-rich fungicides are used. Thousands of tonnes of mercury are emitted annually through these activities. With the Minamata Convention on Mercury entering force this year, increasing regulation of mercury pollution is imminent. It is therefore critical to provide inexpensive and scalable mercury sorbents. The research herein addresses this need by introducing low-cost mercury sorbents made solely from sulfur and unsaturated cooking oils. A porous version of the polymer was prepared by simply synthesising the polymer in the presence of a sodium chloride porogen. The resulting material is a rubber that captures liquid mercury metal, mercury vapour, inorganic mercury bound to organic matter, and highly toxic alkylmercury compounds. Mercury removal from air, water and soil was demonstrated. Because sulfur is a by-product of petroleum refining and spent cooking oils from the food industry are suitable starting materials, these mercury-capturing polymers can be synthesised entirely from waste and supplied on multi-kilogram scales. This study is therefore an advance in waste valorisation and environmental chemistry.

A "circularisation" method to repair deformations and determine the centre of velocity map images.

A problem besetting the analysis of velocity map images, particularly those of photoelectrons, is the presence of distortions that cause the features in the image to deviate from circularity, leading to a loss of resolution in the spectrum extracted. A method is presented to repair such distortions based on fitting the angular behaviour of each of the ring structures to a trigonometric expansion. The repair function allows the intensity at any value of radius and angle to be mapped to a new position that removes the distortion and returns the features to circular. While the method relies on the analysis of the structure in an image, it could also be applied to determine the "repair function" using a calibration image (or series of images) for the experiment. Once the image has been circularised it can be processed by any of the approaches that have been developed for that purpose. The analysis also enables the image centre to be determined with high accuracy. The fitting method utilises an inverse Abel transformation of the image in polar coordinates as a means to reshape the image into a series of spectral features in order to determine the radial position of features at each angle. Although the velocity distribution is not in general spherically symmetric and so this is not a mathematically correct means to extract the velocity distribution, the feature positions are accurately reproduced in the resulting spectrum while the intensity and anisotropy parameters can be remarkably close to those obtained using the proper inverse Abel transformation of the image.

First spectroscopic observation of gold(i) butadiynylide: Photodetachment velocity map imaging of the AuC4H anion.

The velocity map imaging technique was used in the investigation of gold(i) butadiynylide, AuC4H(-), with images recorded at two excitation wavelengths. The resultant photodetachment spectra show a well defined vibrational progression in the neutral with an energy spacing of 343 ± 3 cm(-1). The adiabatic electron affinity was determined to be 1.775 ± 0.005 eV and assigned to the X(1)Σ(+)←X(2)Σ(+) transition between the anionic and neutral ground states. Franck-Condon simulations performed on density functional theory optimized geometries assisted the assignment of linear geometries to the neutral and anion and the observed vibrational progression to that of the Au-C4H stretch.

Fluid dynamic lateral slicing of high tensile strength carbon nanotubes.

Lateral slicing of micron length carbon nanotubes (CNTs) is effective on laser irradiation of the materials suspended within dynamic liquid thin films in a microfluidic vortex fluidic device (VFD). The method produces sliced CNTs with minimal defects in the absence of any chemical stabilizers, having broad length distributions centred at ca 190, 160 nm and 171 nm for single, double and multi walled CNTs respectively, as established using atomic force microscopy and supported by small angle neutron scattering solution data. Molecular dynamics simulations on a bent single walled carbon nanotube (SWCNT) with a radius of curvature of order 10 nm results in tearing across the tube upon heating, highlighting the role of shear forces which bend the tube forming strained bonds which are ruptured by the laser irradiation. CNT slicing occurs with the VFD operating in both the confined mode for a finite volume of liquid and continuous flow for scalability purposes.

Torsion-vibration coupling in S1 toluene: Implications for IVR, the torsional barrier height, and rotational constants.

We have examined the S1←S0 transition of toluene in the region from the 0(0)(0) band to ∼210 cm(-1) above it. The spectrum reveals methyl rotor levels of 0(0) toluene up to m = 6 and of the lowest frequency vibration, 20(1), up to m = 4. The rotor levels of both 20(1) and 0(0) are perturbed by torsion-vibration coupling. The inclusion of torsion-vibration coupling leads to the S1 torsional barrier, V6, being revised from -26.376 cm(-1) to -5.59 cm(-1). The torsion-vibration coupling constant is determined to be 21.1 cm(-1). This situation is the S1 analogue of that recently reported for S0 toluene [Gascooke et al., J. Chem. Phys. 142, 024315 (2015)]. Torsion-vibration coupling alters both the rotor band positions and the rotational contours, which particularly affects the rotational constants associated with motion around the a-axis, about which the methyl group rotates. Every vibrational state (indicated generically by X) will be involved in the corresponding X - X20(1) torsion-vibration coupling; so, this interaction permeates the vib-rotor manifold, providing a mechanism to enhance intramolecular vibrational energy redistribution.

Direct observation of methyl rotor and vib-rotor states of S0 toluene: a revised torsional barrier due to torsion-vibration coupling.

We report a two dimensional, laser induced fluorescence study of the lowest 345 cm(-1) region of S0 toluene. Methyl rotor levels of 00 up to m = 6 and of 201 up to m = 4 are observed. The rotor levels of 00 and 201 have quite different energy spacings that are well fit by a model that includes strong torsion-vibration coupling between them. The model requires that the rotor barrier height be revised from -4.84 cm(-1) (methyl hydrogens in a staggered conformation) to +1.57 cm(-1) (eclipsed conformation). However, the 3a2″ state lies below the 3a1″ state as expected for a staggered conformation due to energy shifts associated with the torsion-vibration coupling. It is shown that the rotor wave-functions exhibit little localization at the torsional energy minima. The variation in the m = 0 wavefunction probability distribution with torsional angle is shown to be very similar for the previously accepted negative V6 value and the torsion-vibration coupling model as this coupling shifts the phase of the wavefunction by 30° compared with its phase for V6 alone. The presence of a strong Δυ = ± 1 torsion-vibration coupling involving the lowest frequency vibrational mode provides a potential pathway for rapid intramolecular vibrational energy redistribution at higher energies.

Influence of cationic surfactants on the formation and surface oxidation states of gold nanoparticles produced via laser ablation.

We report on the time evolution of gold nanoparticles produced by laser ablation in the presence of the cationic surfactants cetyltrimethylammonium bromide (CTAB) and cetyltrimethylammonium chloride (CTAC) in aqueous solution. The broader applicability of a laser-induced nanoparticle formation kinetic model previously developed by us for the case of anionic surfactants in aqueous solution [ J. Phys. Chem. C 2010 , 114 , 15931 - 15940 ] is shown to also apply in the presence of cationic surfactants. We explore the surface properties of the nanoparticles produced in the presence of the cationic surfactants via synchrotron X-ray photoelectron spectroscopy (XPS). The XPS data indicate that at CTA(+) concentrations approximating the aqueous critical micelle concentration Au(III) is present on the nanoparticle surface. Such oxidation is not observed at (i) lower CTA(+) concentrations, (ii) in the presence of an anionic surfactant, or (iii) in the case of pure water as a solvent.