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In the pursuit of more efficient gas turbine engines, components are required to operate for longer times at elevated temperatures. This increased time in service, together with a complex loading regime, can expose the material to environmental attack. This work has demonstrated that the interaction of stress, NaCl and a sulphur-containing environment is critical to cause crack initiation in the early stages of the exposure and accelerated corrosion rates in CMSX-4 at 550°C. The effect of having small concentrations of moisture in the gaseous environment or as water crystallisation in the salt is still to be investigated. A working hypothesis is that the interaction of alkali chlorides with a sulphur-containing atmosphere is the trigger to a self-sustaining cycle where metal chloride formation, vaporisation and oxidation lead to high amounts of hydrogen injection in a rapid manner and, therefore, hydrogen embrittlement.

David Thouless was one of the leading theoretical condensed matter physicists of his generation. He pointed out (with Kosterlitz) that two-dimensional or quasi-two-dimensional physical systems undergo a completely novel type of phase transition; he developed a highly original approach to the theory of localization of electrons in disordered solids; and with his co-authors pioneered the use of topological considerations in the analysis of many-body systems, a technique that gives a very intuitive understanding of the quantum Hall effect and is at the basis of the modern field of topological insulators and superconductors. In 2016 he was awarded the Nobel Prize in physics for ‘theoretical discoveries of topological phase transitions and topological phases of matter’.

Single crystal material, of CMSX-4® alloy composition, was cast and secondary orientation was controlled at the machining stage, to produce c-ring cross-section tubes with known crystallographic orientations. The c-ring tubes were coated with NaCl before being subject to loading up to 700MPa and heated for durations of up to 2 hrs at 550°C in flowing environments containing air and SO2. No cracking was observed in short term tests that were run in the absence of either NaCl, or SO2, indicating a symbiotic interaction is required to initiate cracking. Experiments confirm the presence of oxygen, chlorine and sulphur at the crack tips, formed along {001} crystallographic planes, however, they were distributed discretely, with several oxide and sulphide phases observed. In this work, we image, analyse and identify the phases formed during the cracking and corrosion of CMSX-4® superalloy and hypothesise on the complex chemical interactions that take place during crack initiation.

Plexcitonic antenna complexes, inspired by photosynthetic light-harvesting complexes, are formed by attachment of chlorophylls (Chl) to poly(cysteine methacrylate) (PCysMA) scaffolds grown by atom-transfer radical polymerisation from gold nanostructure arrays. In these pigment-polymer antenna complexes, localised surface plasmon resonances on gold nanostructures are strongly coupled to Chl excitons, yielding hybrid light-matter states (plexcitons) that are manifested in splitting of the plasmon band. Modelling of the extinction spectra of these systems using a simple coupled oscillator model indicates that their coupling energies are up to twice as large as those measured for LHCs from plants and bacteria. Coupling energies are correlated with the exciton density in the grafted polymer layer, consistent with the collective nature of strong plasmon-exciton coupling. Steric hindrance in fully-dense PCysMA brushes limits binding of bulky chlorophylls, but the chlorophyll concentration can be increased to ∼2 M, exceeding that in biological light-harvesting complexes, by controlling the grafting density and polymerisation time. Moreover, synthetic plexcitonic antenna complexes display pH- and temperature-responsiveness, facilitating active control of plasmon-exciton coupling. Because of the wide range of compatible polymer chemistries and the mild reaction conditions, plexcitonic antenna complexes may offer a versatile route to programmable molecular photonic materials. This journal is

Soon after the discovery of superconductivity in Sr2RuO4 (SRO) a quarter-century ago, it was conjectured that its order parameter (OP) has a form similar to that realized in the superfluid phases of 3-He, namely, odd parity and spin triplet. While the chiral p-wave pairing believed to be realized in the A phase of that system was favored by several early experiments, in particular, the muon spin rotation and the Knight shift measurements published in 1998, the original Knight shift result was called into question in early 2019, raising the question as to whether the “chiral p-wave”, or even the spin-triplet pairing itself, is indeed realized in SRO. In this brief pedagogical review, we will address this question by counterposing the currently accepted results of Knight shift, polarized neutron scattering, spin counterflow half-quantum vortex (HQV), and Josephson experiments, which probe the spin and orbital parts of the OP, respectively, with predictions made both by standard BCS theory and by more general arguments based only on (1) the symmetry of the Hamiltonian including the spin-orbital terms, (2) thermodynamics, and (3) the qualitative experimental features of the material. In the hope of enhancing readers’ intuitive grasp of these arguments, we introduce a notation for triplet states alternative to the more popular “d-vector” one which we believe well suited to SRO. We conclude that the most recent Knight shift and polarized neutron scattering experiments do not exclude in the bulk the odd-parity, spin-triplet “helical” states allowed by the symmetry group of SRO but do exclude the “chiral p-wave”, ${{{\varGamma }}}_{5}^{-}$ state. On the other hand, the Josephson and in-plane-magnetic-field stabilized HQV experiments showed that the pairing symmetry in SRO cannot be of the even-parity, spin-singlet type, and furthermore, that in the surface region or in samples of mesoscopic size the d-vector must be along the c axis, thus excluding all bulk p-wave states except ${{{\varGamma }}}_{5}^{-}$ . Possible resolution of this rather glaring prima facie contradiction is discussed, taking into account implications of other important experiments on SRO, including that of the muon spin rotation, which are touched upon briefly only towards the end of this article.

I present some rather selective reminiscences of my long career in physics, from my doctoral work to the present. I do not spend time on topics such as the nuclear magnetic resonance behavior of 3He, as I have reviewed the history extensively elsewhere, but rather concentrate, first, on my long-running project to make condensed matter physics relevant to questions in the foundations of quantum mechanics, and second, on various rather “quirky” problems such as an attempt to amplify the effects of the parity violation due to the weak interaction to a macroscopic level, and an unconventional proposal for the mechanism of the first-order phase transition between the A and B phases of superfluid liquid 3He.

Magnetically-sensitive experiments and newly-developed quantum technologies with integrated high-permeability magnetic shields require increasing control of their magnetic field environment and reductions in size, weight, power and cost. However, magnetic fields generated by active components are distorted by high-permeability magnetic shielding, particularly when they are close to the shield's surface. Here, we present an efficient design methodology for creating desired static magnetic field profiles by using discrete coils electromagnetically-coupled to a cylindrical passive magnetic shield. We utilize a modified Green's function solution that accounts for the interior boundary conditions on a closed finite-length high-permeability cylindrical magnetic shield, and determine simplified expressions when a cylindrical coil approaches the interior surface of the shield. We use an analytic formulation of simple discrete building blocks to provide a complete discrete coil basis to generate any physically-attainable magnetic field inside the shield. We then use a genetic algorithm to find optimized discrete coil structures composed of this basis. We use our methodology to generate an improved linear axial gradient field, $\mathrm{d}B_z/\mathrm{d}z$, and transverse bias field, $B_x$. These optimized structures increase, by a factor of seven and three compared to the standard configurations, the volume in which the desired and achieved fields agree within $1\%$ accuracy, respectively. This coil design method can be used to optimize active--passive magnetic field shaping systems that are compact and simple to manufacture, enabling accurate magnetic field control in spatially-confined experiments at low cost., Comment: The authors M. Packer and P. J. Hobson have contributed equally to this work. 24 pages, 16 figures

A model system for the investigation of diffusional transport in compartmentalized nanosystems is described. Arrays of "corrals" enclosed within poly[oligo(ethylene glycol)methyl ether methacrylate] (POEGMA) "walls" were fabricated using double-exposure interferometric lithography to deprotect aminosilane films protected by a nitrophenyl group. In exposed regions, removal of the nitrophenyl group enabled attachment of an initiator for the atom-transfer radical polymerization of end-grafted POEGMA (brushes). Diffusion coefficients for poly(ethylene glycol) in these corrals were obtained by fluorescence correlation spectroscopy. Two modes of surface diffusion were observed: one which is similar to diffusion on the unpatterned surface and a very slow mode of surface diffusion that becomes increasingly important as confinement increases. Diffusion within the POEGMA brushes does not significantly contribute to the results.

When light-harvesting complex II (LHCII), isolated from spinach, is adsorbed onto arrays of gold nanostructures formed by interferometric lithography, a pronounced splitting of the plasmon band is observed that is attributable to strong coupling of the localised surface plasmon resonance to excitons in the pigment-protein complex. The system is modelled as coupled harmonic oscillators, yielding an exciton energy of 2.24 ± 0.02 eV. Analysis of dispersion curves yields a Rabi energy of 0.25 eV. Extinction spectra of the strongly coupled system yield a resonance at 1.43 eV that varies as a function of the density of nanostructures in the array. The enhanced intensity of this feature is attributed to strong plasmon-exciton coupling. Comparison of data for a large number of light-harvesting complexes indicates that by control of the protein structure and/or pigment compliment it is possible to manipulate the strength of plasmon-exciton coupling. In strongly coupled systems, ultra-fast exchange of energy occurs between pigment molecules: coherent coupling between non-local excitons can be manipulated via selection of the protein structure enabling the observation of transitions that are not seen in the weak coupling regime. Synthetic biology thus provides a means to control quantum-optical interactions in the strong coupling regime.

Is there sufficient evidence that mindfulness training is ready to be implemented in schools? Going beyond the relatively comprehensive literature on mindfulness and mental health, here we investigate whether mindfulness can help students learn. We begin by drawing on laboratory studies in experimental psychology and cognitive science, and then reflect on research conducted in schools and other applied contexts. We also briefly discuss key insights from the neuroscience of mindfulness, and compare mindfulness to other well- known learning interventions. Our review suggests that mindfulness interventions have the potential to make students more focused, to help them regulate their emotions, to be more flexible and creative, and to change their brains in a way that encourages greater conscious control of their thoughts, feelings, and actions. These findings indicate that mindfulness may improve cognitive abilities that are key to learning outcomes, and may have a complementary relationship with other interventions such as retrieval practice. Field experiments also show promise, and are indicative of high feasibility, low risk, and suggest generalisability across diverse groups, ages, genders, and cultures. However, most studies currently lack standardisation, active control groups, and more experiments are needed that explicitly focus on academic performance in schools. We conclude by providing practical advice and best practices for the implementation of mindfulness training in schools, and highlight the promising future of digital mindfulness-based interventions as a scalable and affordable way to implement mindfulness in educational contexts. This review will be of value to those who are interested in the application of mindfulness to learning contexts, but also researchers and others who wish to know the current state of scientific evidence on mindfulness-based interventions and their impact on learning.

Binary brush structures consisting of poly(cysteine methacrylate) (PCysMA) “corrals” enclosed within poly(oligoethylene glycol methyl ether methacrylate) (POEGMA) “walls” are fabricated simply and efficiently using a two-step photochemical process. First, the C–Cl bonds of 4-(chloromethyl)phenylsilane monolayers are selectively converted into carboxylic acid groups by patterned exposure to UV light through a mask and POEGMA is grown from unmodified chlorinated regions by surface-initiated atom-transfer radical polymerisation (ATRP). Incorporation of a ratiometric fluorescent pH indicator, Nile Blue 2-(methacryloyloxy)ethyl carbamate (NBC), into the polymer brushes facilitates assessment of local changes in pH using a confocal laser scanning microscope with spectral resolution capability. Moreover, the dye label acts as a radical spin trap, enabling removal of halogen end-groups from the brushes via in situ dye addition during the polymerisation process. Second, an initiator is attached to the carboxylic acid-functionalised regions formed by UV photolysis in the patterning step, enabling growth of PCysMA brushes by ATRP. Transfer of the system to THF, a poor solvent for PCysMA, causes collapse of the PCysMA brushes. At the interface between the collapsed brush and solvent, selective derivatisation of amine groups is achieved by reaction with excess glutaraldehyde, facilitating attachment of aminobutyl(nitrile triacetic acid) (NTA). The PCysMA brush collapse is reversed on transfer to water, leaving it fully expanded but only functionalized at the brush–water interface. Following complexation of NTA with Ni2+, attachment of histidine-tagged proteorhodopsin and lipid deposition, light-activated transport of protons into the brush structure is demonstrated by measuring the ratiometric response of NBC in the POEGMA walls.

The recent ExecutiveOrder by President Trump attempting to ban temporarily the citizens of seven countries (Iran, Iraq, Libya, Somalia, Sudan, Syria, and Yemen) from entering the United States is having significant consequences within the country and around the world. The Order poses a threat to the health and vitality of science, barring students and scientists from these countries from traveling to the United States to study or to attend conferences. In preventing those members of the international scientific community from traveling beyond U.S. borders without guaranteed safe return, the Executive Order demeans them; in so doing, it demeans us all. Universities and research communities are especially impacted, as major universities have students and often faculty holding passports from one of these seven countries. This temporary ban would affect refugees fleeing war-torn areas, challenging the long-standing notion that the United States is a safe haven for those fleeing persecution and war in addition to being a magnet for talent from every corner of the world. The pages of this journal reflect the geographic, ethnic, and cultural diversity that underpins great science. The ban impacts domestic and global scientific efforts and communities. Science succeeds through the cooperation between collections of individuals and teams around the world discovering and learning from each other. To ensure rapid scientific progress, open communication and exchange between scientists are essential. As scientists, engineers, and clinicians, we have benefited from open interactions and collaborations with visitors and students from all parts of the world as well as through scientific publications and discussions at scientific meetings.

The diffusion of a polyzwitterion, poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC), in aqueous solution containing different alkali halides was studied by fluorescence correlation spectroscopy at single molecule level. It was found that the halide anion has a greater effect on the radius of zwitterionic PMPC molecules than alkali cations, which is due to the mechanism by which PMPC molecules interact with the surrounding hydrogen bond network of water molecules and adsorbed ions. With the addition of salt, the size of PMPC remains constant while its diffusion coefficient is reduced slightly, although larger cations (e.g. K+) result in slightly increased diffusion coefficient for 1 M potassium chloride-based solutions. This enhanced diffusion coefficient is attributed to the decrease in the viscosity of the aqueous solution on the addition of salt. When the counter-ion was varied in potassium-based salts, different effects were observed for different anions, resulting a reduction in the diffusion coefficient as a function of salt concentration. This reduction was modest for KBr, but significant for KI. Overall, no discernible changes were observed as the size of the PMPC coil was varied, except in case of KI for which a significant increase was observed at higher ionic strength. Divalent cations (Ca2+ and Mg2+), produced similar effects to those found for monovalent cations. These effects are explained by the interaction of PMPC with the hydrogen bond network of water molecules and with the adsorbed ions.

Gas turbines blades are required to operate at high temperatures while being subjected to stress and corrosive environments. These demanding conditions have led to the need to better understand the interactions between corrosion and loading in order to improve lifing algorithms used for service interval predictions. A new crack growth measurement technique involving direct current potential difference (PD) has been developed for use in these harsh conditions. A good correlation between PD signal and crack area has been achieved. Estimations of the crack depth have been made based on fracture surface imaging, these experimentally measured crack depth propagation rates have been compared with Paris law predictions. A stress intensity factor (SIF) interaction between multiple cracks was found, where the SIF is enhanced when cracks become close. It was found that both the fatigue cycle rate and the crack shape appear to influence the SIF magnitude and the crack depth at which specimens fail, or initiate into crack propagation which is consistent with fatigue.

This volume is a collection of papers from the 14th International Symposium on Superalloys, held on September 12–16, 2021 Although evidence exists of the potential impact of stress, co-incident with corrosive environments at high temperature, for single crystal turbine blades, the mechanism responsible is not fully understood. This work explores the effect of CaSO4, Na2SO4 and sea salt on the scale formation and crack initiation of CMSX-4 at 550°C in 50 ppm of SO2 and synthetic air under a static stress of 800 MPa. The cross-sectional analysis showed that the CaSO4 and the Na2SO4 salted specimens did not undergo a significant degree of corrosion degradation and no cracks were detected after 400 hours of exposure. However, sea salt caused significant degradation to the scale and cracks were detected by X-ray CT scanning after 400 hours of exposure. The findings from this study suggests that the sulfation of chlorine containing species in sea salt led to the formation, vaporisation and re-oxidation of metal chlorides and this mechanism was found to play a key role in the formation of a non-protective scale. An active oxidation mechanism has been proposed to interpret the results. In conclusion, it is hypothesized that due to the synergistic effect of stress and the formation of a non-protective scale, fast diffusion paths for sulfur, oxygen and chlorine ingress were formed. Further work is currently being undertaken to understand the effect of these species on the local embrittlement of CMSX-4 that ultimately led to the initiation of cracks in the specimen.

Author(s): Bai, Shuming; Balevicius, Vytautas; Bittner, Eric; Cheng, Yuan-Chung; Chergui, Majed; Cina, Jeffrey; das Neves Rodrigues, Natercia; Datta, Animesh; Dawlaty, Jahan; Dodin, Amro; Fingerhut, Benjamin; Fleming, Graham; Ginsberg, Naomi; Hammes-Schiffer, Sharon; Huxter, Vanessa; Kohler, Bern; Lee, Yumin; Leggett, Graham; Marcus, Andrew; Morenz, Karen; Ogilvie, Jennifer; Olaya-Castro, Alexandra; Oliver, Thomas AA; Son, Minjung; Song, Yin; Stavros, Vasilios

We uncover a novel phenomenon from a recent artificial light-harvesting experiment [P.-Z. Chen et al., Angew. Chem., Int. Ed. Engl. 55, 2759 (2016)] on organic nanocrystals of self-assembled difluoroboron chromophores. A resonant confinement of a polariton under strong photon-exciton coupling is predicted to exist within the microcavity of the crystal's own natural boundaries. Moreover, the radiative energy of a localized exciton falls into the spectrum of confinement. Hence, in the experiment, the spontaneous emission of an excited pigment would undergo a two-step process. It should first decay to an excitonic polariton trapped by the cavity resonance. The intermediate polariton could then funnel the energy directly to a doped acceptor, leading to the over 90% transfer efficiency observed at less than $1/1000\text{ }\text{ }\text{ }\mathrm{acceptor}/\mathrm{donor}\text{ }\mathrm{ratio}$. The proposed mechanism is supported by parameter-free analyses entirely based on experiment data. Our finding may imply possible polariton-mediated pathways for energy transfers in biological photosynthesis.

Uranium extracted from seawater is a promising source of uranium for nuclear energy, and the extraction technology using polymer sorbents has been shown to be feasible. However, improving selectivity for uranium over other metals, notably vanadium and iron, is essential to increase efficiency and reduce costs. In the present work, the kinetics of the binding of these three metals with glutaroimide-dioxime as a molecular analogue of polymer sorbents has been studied using stopped-flow and conventional UV Visible absorption spectroscopy to monitor the reactions over a range of time scales. Qualitatively, vanadium reacts the slowest of the three metals despite being able to form a very strong complex, with the 1 : 2 vanadium/ligand complex forming over weeks, likely due to the slow hydrolysis of the strong oxido ligands, while iron reacts fast and uranyl faster still, despite the presence of carbonate in the uranyl species. Conditional rate constants were determined for the formation of 1 : 1 glutaroimide-dioxime complexes with the three metal ions. Besides, in a narrow and near neutral pH region, a rate equation for the formation of the 1 : 1 vanadium/glutaroimide-dioxime complex was developed, showing the reaction is the first order with respect to [V], [ligand], and [H+]. These observations, some being qualitative and others quantitative, are consistent with previous marine tests of polymer adsorbents, and give mechanistic insight into how glutaroimide-dioxime forms complexes with uranium, iron, and vanadium.

The site-specific immobilization of histidine-tagged proteins to patterns formed by far-field and near-field exposure of films of aminosilanes with protein-resistant photolabile protecting groups is demonstrated. After deprotection of the aminosilane, either through a mask or using a scanning near-field optical microscope, the amine terminal groups are derivatized first with glutaraldehyde and then with N-(5-amino-1-carboxypentyl)iminodiacetic acid to yield a nitrilo-triacetic-acid-terminated surface. After complexation with Ni(2+), this surface binds histidine-tagged GFP and CpcA-PEB in a site-specific fashion. The chemistry is simple and reliable and leads to extensive surface functionalization. Bright fluorescence is observed in fluorescence microscopy images of micrometer- and nanometer-scale patterns. X-ray photoelectron spectroscopy is used to study quantitatively the efficiency of photodeprotection and the reactivity of the modified surfaces. The efficiency of the protein binding process is investigated quantitatively by ellipsometry and by fluorescence microscopy. We find that regions of the surface not exposed to UV light bind negligible amounts of His-tagged proteins, indicating that the oligo(ethylene glycol) adduct on the nitrophenyl protecting group confers excellent protein resistance; in contrast, exposed regions bind His-GFP very effectively, yielding strong fluorescence that is almost completely removed on treatment of the surface with imidazole, confirming a degree of site-specific binding in excess of 90%. This simple strategy offers a versatile generic route to the spatially selective site-specific immobilization of proteins at surfaces.

In recent years, the prospective recovery of uranium from seawater has become a topic of interest owing to the increasing demand for nuclear fuel worldwide and because of efforts to find sustainable alternatives to terrestrial mining for uranium. To date, the most advanced and promising method of extracting and concentrating uranium from seawater involves the use of polymeric sorbents containing the amidoxime binding moiety. Among a number of different moieties investigated, glutaroimide-dioxime is the most promising one, forming very stable complexes with U(VI) even in the presence of carbonate. To properly assess the affinity of uranium toward the amidoxime substrates, a comprehensive knowledge of the aqueous chemical equilibria of uranium is required. With this aim, in this paper we review the chemical equilibria of uranium (as UO22+) in seawater, focusing on the solution equilibria leading to the formation of the stable complexes, Mm(UO2)(CO3)3(2m–4)(aq) (M = Ca or Mg, m = 0–2). These binary and terna...

Spent potlining (SPL) hazardous waste is a potentially valuable source of fluoride, which may be recovered through chemical leaching and adsorption with a selective sorbent. For this purpose, the commercially available chelating resin Purolite® S950+ was loaded with lanthanum ions, to create a novel ligand-exchange sorbent. The equilibrium fluoride uptake behaviour of the resin was thoroughly investigated, using NaF solution and a simulant leachate of SPL waste. The resin exhibited a large maximum defluoridation capacity of 187 ± 15 mg g−1 from NaF solution and 126 ± 10 mg g−1 from the leachate, with solution pH being strongly influential to uptake performance. Isotherm and spectral data indicated that both chemisorption and unexpected physisorption processes were involved in the fluoride extraction and suggested that the major uptake mechanism differed in each matrix. The resin demonstrates significant potential in the recovery of fluoride from aqueous waste-streams.

I review how, driven originally by foundational concerns and more recently by prospects of quantum computing, the idea of applying quantum mechanics to the motion of macroscopic variables such as the flux in a Josephson qubit went over the last 50 years from a theorists’ pipe-dream to an everyday engineering subject.

Many biological mechanisms can be considered to be low-dimensional systems: their function is determined by molecular objects of reduced dimensionality. Bacterial photosynthesis is a very good example: the photosynthetic pathway is contained within nano-objects (vesicles) whose function is determined by the numbers and nanoscale organization of membrane proteins and by the ratios of the different types of protein that they contain. Systems biology has provided computational models for studying these processes, but there is a need for experimental platforms with which to test their predictions. This Invited Feature Article reviews recent work on the development of tools for the reconstruction of membrane processes on solid surfaces. Photochemical methods provide a powerful, versatile means for the organization of molecules and membranes across length scales from the molecular to the macroscopic. Polymer brushes are highly effective supports for model membranes and versatile functional and structural components in low-dimensional systems. The incorporation of plasmonic elements facilitates enhanced measurement of spectroscopic properties and provides an additional design strategy via the exploitation of quantum optical phenomena. A low-dimensional system that incorporates functional transmembrane proteins and a mechanism for the in situ measurement of proton transport is described.

In strong plasmon-exciton coupling, a surface plasmon mode is coupled to an array of localized emitters to yield new hybrid light-matter states (plexcitons), whose properties may in principle be controlled via modification of the arrangement of emitters. We show that plasmon modes are strongly coupled to synthetic light-harvesting maquette proteins, and that the coupling can be controlled via alteration of the protein structure. For maquettes with a single chlorin binding site, the exciton energy (2.06 ± 0.07 eV) is close to the expected energy of the Qy transition. However, for maquettes containing two chlorin binding sites that are collinear in the field direction, an exciton energy of 2.20 ± 0.01 eV is obtained, intermediate between the energies of the Qx and Qy transitions of the chlorin. This observation is attributed to strong coupling of the LSPR to an H-dimer state not observed under weak coupling.

The diffusion of rhodamine-labeled poly(ethylene glycol) (r-PEG) within surface-grafted poly(ethylene glycol) (s-PEG) layers in aqueous solution at 18 °C was measured by fluorescence correlation spectroscopy. The diffusion coefficient of r-PEG within s-PEG was controlled by the grafting density, σ, and scaled as σ–1.42±0.09. It is proposed that a characteristic blob size associated with the grafted (brush) layer defines the region through which the r-PEG diffusion occurs. The diffusion coefficients for r-PEG in semidilute solution were found to be similar to those in the brushes.

I draw an analogy between the “measurement paradox” of quantum mechanics in 2019 and the “Gibbs paradox” of statistical physics in 1875, and use it to argue that we have good reason to believe that the answer to the question in my title is “no”.

Nanotechnology demands the synthesis of highly precise, functional materials, tailored for specific applications. One such example is bit patterned media. These high-density magnetic data-storage materials require specific and uniform magnetic nanoparticles (MNPs) to be patterned over large areas (cm2 range) in exact nanoscale arrays. However, the realisation of such materials for nanotechnology applications depends upon reproducible fabrication methods that are both precise and environmentally-friendly, for cost-effective scale-up. A potentially ideal biological fabrication methodology is biomineralisation. This is the formation of inorganic minerals within organisms, and is known to be highly controlled down to the nanoscale whilst being carried out under ambient conditions. The magnetotactic bacterium Magnetospirillum magneticum AMB-1 uses a suite of dedicated biomineralisation proteins to control the formation of magnetite MNPs within their cell. One of these proteins, Mms6, has been shown to control formation of magnetite MNPs in vitro. We have previously used Mms6 on micro-contact printed (μCP) patterned self-assembled monolayer (SAM) surfaces to control the formation and location of MNPs in microscale arrays, offering a bioinspired and green-route to fabrication. However, μCP cannot produce patterns reliably with nanoscale dimensions, and most alternative nanofabrication techniques are slow and expensive. Interferometric lithography (IL) uses the interference of laser light to produce nanostructures over large areas via a simple process implemented under ambient conditions. Here we combine the bottom-up biomediated approach with a top down IL methodology to produce arrays of uniform magnetite MNPs (86 ± 21 nm) with a period of 357 nm. This shows a potentially revolutionary strategy for the production of magnetic arrays with nanoscale precision in a process with low environmental impact, which could be scaled readily to facilitate large-scale production of nanopatterned surface materials for technological applications.

A non-oxido V(v) complex with glutaroimide-dioxime (H3L), a ligand for recovering uranium from seawater, was synthesized from aqueous solution as Na[V(L)2]·2H2O, and the structure determined by X-ray diffraction. It is the first non-oxido V(v) complex that has been directly synthesized in and crystallized from aqueous solution. The distorted octahedral structure contains two fully deprotonated ligands (L3-) coordinating to V5+, each in a tridentate mode via the imide N (RV-N = 1.96 A) and oxime O atoms (RV-O = 1.87-1.90 A). Using 17O-labelled vanadate as the starting material, concurrent 17O/51V/1H/13C NMR, in conjunction with ESI-MS, unprecedentedly demonstrated the stepwise displacement of the oxido V 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 1111111111111111111111111111111111 1111111111111111111111111111111111 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 0000000000000000000000000000000000 O bonds by glutaroimide-dioxime and verified the existence of the "bare" V5+/glutaroimide-dioxime complex, [V(L)2]-, in aqueous solution. In addition, the crystal structure of an intermediate 1 : 1 V(v)/glutaroimide-dioxime complex, [VO2(HL)]-, in which the oxido bonds of vanadate are only partially displaced, corroborates the observations by NMR and ESI-MS. Results from this work provide important insights into the strong sorption of vanadium on poly(amidoxime) sorbents in the recovery of uranium from seawater. Also, because vanadium plays important roles in biological systems, the syntheses of the oxido and non-oxido V5+ complexes and the unprecedented demonstration of the displacement of the oxido VO bonds help with the on-going efforts to develop new vanadium compounds that could be of importance in biological applications.

The development of an efficient and economical system for extracting uranium from seawater could lead to an essentially limitless source of fuel for nuclear reactors. Currently, the most promising technology for recovering uranium from seawater involves the use of polymeric sorbents functionalized with the amidoxime moiety. However, competition of amidoxime sorbents with carbonate for uranium, indiscriminate sorption of other seawater cations, seawater temperature, and sorbent durability affect the efficiency and cost of this technology. Insights from thermodynamic and structural studies have proved to be powerful tools for addressing these issues and aiding the development of more effective sorbents for uranium. We summarize herein the results of these studies and discuss their implications for the extraction of uranium from seawater.

Complexation of calcium and magnesium with glutarimidedioxime, a ligand of importance in the sorption of uranium from seawater by functionalized sorbents, in aqueous solutions was investigated with potentiometry and calorimetry. The stability constants of the complexes and the enthalpies of complexation were determined. Results show that calcium(II) and magnesium(II) form much weaker complexes with glutarimidedioxime than uranium(VI). However, due to the very high concentrations of calcium and magnesium in seawater, small but significant fractions of the sorption sites on the glutarimidedioxime-functionalized sorbent are expected to be occupied by calcium and magnesium. Results also show that the dominant complexation reactions of calcium and magnesium with glutarimidedioxime at seawater pH are endothermic processes, implying that the complexation, as well as the sorption of calcium and magnesium on the glutarimidedioxime-functionalized sorbent, would be enhanced at higher temperatures.

The photocatalytic self-cleaning characteristics of titania facilitate the fabrication of reuseable templates for protein nanopatterning. Titania nanostructures were fabricated over square centimeter areas by interferometric lithography (IL) and nanoimprint lithography (NIL). With the use of a Lloyd's mirror two-beam interferometer, self-assembled monolayers of alkylphosphonates adsorbed on the native oxide of a Ti film were patterned by photocatalytic nanolithography. In regions exposed to a maximum in the interferogram, the monolayer was removed by photocatalytic oxidation. In regions exposed to an intensity minimum, the monolayer remained intact. After exposure, the sample was etched in piranha solution to yield Ti nanostructures with widths as small as 30 nm. NIL was performed by using a silicon stamp to imprint a spin-cast film of titanium dioxide resin; after calcination and reactive ion etching, TiO2 nanopillars were formed. For both fabrication techniques, subsequent adsorption of an oligo(ethylene glycol) functionalized trichlorosilane yielded an entirely passive, protein-resistant surface. Near-UV exposure caused removal of this protein-resistant film from the titania regions by photocatalytic degradation, leaving the passivating silane film intact on the silicon dioxide regions. Proteins labeled with fluorescent dyes were adsorbed to the titanium dioxide regions, yielding nanopatterns with bright fluorescence. Subsequent near-UV irradiation of the samples removed the protein from the titanium dioxide nanostructures by photocatalytic degradation facilitating the adsorption of a different protein. The process was repeated multiple times. These simple methods appear to yield durable, reuseable samples that may be of value to laboratories that require nanostructured biological interfaces but do not have access to the infrastructure required for nanofabrication.

Poly(oligoethylene glycol methyl ether methacrylate) (POEGMEMA) brushes, grown from silicon oxide surfaces by surface-initiated atom transfer radical polymerization (SI-ATRP), were end-capped by reaction with sodium azide leading to effective termination of polymerization. Reduction of the terminal azide to an amine, followed by derivatization with the reagent of choice, enabled end-functionalization of the polymers. Reaction with bromoisobutryl bromide yielded a terminal bromine atom that could be used as an initiator for ATRP with a second, contrasting monomer (methacrylic acid). Attachment of a nitrophenyl protecting group to the amine facilitated photopatterning: when the sample was exposed to UV light through a mask, the amine was deprotected in exposed regions, enabling selective bromination and the growth of a patterned brush by ATRP. Using this approach, micropatterned pH-responsive poly(methacrylic acid) (PMAA) brushes were grown on a protein resistant planar poly(oligoethylene glycol methyl ether methacrylate) (POEGMEMA) brush. Atomic force microscopy analysis by tapping mode and PeakForce quantitative nanomechanical mapping (QNM) mode allowed topographical verification of the spatially specific secondary brush growth and its stimulus responsiveness. Chemical confirmation of selective polymer growth was achieved by secondary ion mass spectrometry (SIMS).

Poly(2-dimethylamino)ethyl methacrylate) (PDMA) brushes are grown from planar substrates via surface atom transfer radical polymerization (ATRP). Quaternization of these brushes is conducted using 1-iodooctadecane in n-hexane, which is a non-solvent for PDMA. Ellipsometry, AFM, and water contact angle measurements show that surface-confined quaternization occurs under these conditions, producing pH-responsive brushes that have a hydrophobic upper surface. Systematic variation of the 1-iodooctadecane concentration and reaction time enables the mean degree of surface quaternization to be optimized. Relatively low degrees of surface quaternization (ca. 10 mol % as judged by XPS) produce brushes that enable the formation of supported lipid bilayers, with the hydrophobic pendent octadecyl groups promoting in situ rupture of lipid vesicles. Control experiments confirm that quaternized PDMA brushes prepared in a good brush solvent (THF) produce non- pH-responsive brushes, presumably because the pendent octadecyl groups form micelle-like physical cross-links throughout the brush layer. Supported lipid bilayers (SLBs) can also be formed on the non-quaternized PDMA precursor brushes, but such structures proved to be unstable to small changes in pH. Thus, surface quaternization of PDMA brushes using 1-iodooctadecane in n-hexane provides the best protocol for the formation of robust SLBs. Fluorescence recovery after photobleaching (FRAP) studies of such SLBs indicate diffusion coefficients (2.8 ± 0.3 μ ms −1 ) and mobile fractions (98 ± 2%) that are comparable to the literature data reported for SLBs prepared directly on planar glass substrates.