Quantum Nature of Charge Transport in Inkjet-Printed Graphene Revealed in High Magnetic Fields up to 60T.

Inkjet-printing of graphene, iGr, provides an alternative route for the fabrication of highly conductive and flexible graphene films for use in devices. However, the contribution of quantum phenomena associated with 2D single layer graphene, SLG, to the charge transport in iGr is yet to be explored. Here, the first magneto-transport study of iGr in high magnetic fields up to 60 T is presented. The observed quantum phenomena, such as weak localization and negative magnetoresistance, are strongly affected by the thickness of the iGr film and can be explained by a combination of intra- and inter-flake classical and quantum charge transport. The quantum nature of carrier transport in iGr is revealed using temperature, electric field, and magnetic field dependences of the iGr conductivity. These results are relevant for the exploitation of inkjet deposition of graphene, which is of particular interest for additive manufacturing and 3D printing of flexible and wearable electronics. It is shown that printed nanostructures enable ensemble averaging of quantum interference phenomena within a single device, thereby facilitating comparison between experiment and underlying statistical models of electron transport.

The role of covalency in enhancing stability of Eu and Am complexes: a DFT comparison of BTP and BTPhen.

We compare the stabilities and bonding nature of [Eu/Am(BTPhen)2(NO3)]2+ complexes to those previously reported for [Eu/Am(BTP)3]3+, and investigate whether more accurately reflecting the reaction conditions of the separation process by considering [Eu/Am(NO3)3(H2O)x] (x = 3, 4) complexes instead of aquo complexes increases the selectivity of the separation ligands BTP and BTPhen for Am over Eu. The geometric and electronic structures of [Eu/Am(BTPhen)2(NO3)]2+ and [Eu/Am(NO3)3(H2O)x] (x = 3, 4) have been evaluated using density functional theory (DFT) and used as the basis for analysis of the electron density through the application of the quantum theory of atoms in molecules (QTAIM). Increased covalent bond character for the Am complexes of BTPhen over Eu analogues was found, with this increase more pronounced than that found in BTP complexes. BHLYP-derived exchange reaction energies were evaluated using the hydrated nitrates as a reference and a favourability for actinide complexation by both BTP and BTPhen was found, with the BTPhen ligand found to be more selective, with relative stability ≈0.17 eV greater than BTP.

Photosensitisation of inkjet printed graphene with stable all-inorganic perovskite nanocrystals.

All-inorganic perovskite nanocrystals (NCs) with enhanced environmental stability are of particular interest for optoelectronic applications. Here we report on the formulation of CsPbX3 (X is Br or I) inks for inkjet deposition and utilise these NCs as photosensitive layers in graphene photodetectors, including those based on single layer graphene (SLG) as well as inkjet-printed graphene (iGr) devices. The performance of these photodetectors strongly depends on the device structure, geometry and the fabrication process. We achieve a high photoresponsivity, R > 106 A W-1 in the visible wavelength range and a spectral response controlled by the halide content of the perovskite NC ink. By utilising perovskite NCs, iGr and gold nanoparticle inks, we demonstrate a fully inkjet-printed photodetector with R ≈ 20 A W-1, which is the highest value reported to date for this type of device. The performance of the perovskite/graphene photodetectors is explained by transfer of photo-generated charge carriers from the perovskite NCs into graphene and charge transport through the iGr network. The perovskite ink developed here enabled realisation of stable and sensitive graphene-based photon detectors. Compatibility of inkjet deposition with conventional Si-technologies and with flexible substrates combined with high degree of design freedom provided by inkjet deposition offers opportunities for partially and fully printed optoelectronic devices for applications ranging from electronics to environmental sciences.

Functionalized Gold Nanoparticles with a Cohesion Enhancer for Robust Flexible Electrodes.

The development of conductive inks is required to enable additive manufacturing of electronic components and devices. A gold nanoparticle (AuNP) ink is of particular interest due to its high electrical conductivity, chemical stability, and biocompatibility. However, a printed AuNP film suffers from thermally induced microcracks and pores that lead to the poor integrity of a printed electronic component and electrical failure under external mechanical deformation, hence limiting its application for flexible electronics. Here, we employ a multifunctional thiol as a cohesion enhancer in the AuNP ink to prevent the formation of microcracks and pores by mediating the cohesion of AuNPs via strong interaction between the thiol groups and the gold surface. The inkjet-printed AuNP electrode exhibits an electrical conductivity of 3.0 × 106 S/m and stable electrical properties under repeated cycles (>1000) of mechanical deformation even for a single printed layer and in a salt-rich phosphate-buffered saline solution, offering exciting potential for applications in flexible and 3D electronics as well as in bioelectronics and healthcare devices.

Assessment and Revision of the Veterinary Internship and Residency Matching Program Standardized Letter of Reference.

The Veterinary Internship and Residency Matching Program (VIRMP) recently revised its electronic standardized letter of reference (SLOR) to improve the quality and usefulness of the data obtained from it and to enhance the relevance of non-cognitive and cognitive candidate attributes assessed. We used a stepwise process including a broad survey of SLOR readers and writers, analysis of past SLORs, and a multi-wave iterative revision that included key stakeholders, such as residency and internship program directors from academia and private practice. Data from the SLOR survey and analysis of past SLOR responses identified opportunities to improve applicant differentiation, mitigate positive bias, and encourage response consistency. The survey and other analytics identified and confirmed performance domains of high relevance. The revised SLOR assesses four performance domains: knowledge base and clinical skills, stress and time management, interpersonal skills, and personal characteristics. Ratings within the revised SLOR are predominantly criterion-referenced to enhance discernment of candidate attributes contained within each domain. Questions assessing areas of strength and targeted mentoring were replaced with free-text boxes, which allow writers to comment on positive and neutral/negative ratings of attributes within domains. Minor revisions were made to certain questions to enhance readability, streamline responses, or address targeted concerns identified in the SLOR survey or stakeholder review. The revised SLOR was deployed in the 2020 VIRMP; data from a survey of writers (n = 647) and readers (n = 378) indicate that the redesign objectives were achieved.

Thermal and Photochemical Reduction and Functionalization Chemistry of the Uranyl Dication, [UVIO2]2.

The uranyl ion, [UVIO2]2+, possesses rigorously trans, strongly covalent, and chemically robust U-oxo groups. However, through the use of anaerobic reaction techniques, both one- and two-electron reductive functionalization of the uranyl oxo groups has been discovered and developed. Prior to 2010, this unusual reactivity centered around the reductive silylation of the uranyl ion which entailed conversion of the oxo ligands into siloxy ligands and reductive metalation of the uranyl oxo with Group 1 and f-block metals. This review surveys the large number of new examples of reductive functionalization of the uranyl ion that have been reported since 2010, including reductive borylation and alumination, metalation with d- or f-block metals, and new examples of reductive silylation. Other examples of oxo-group functionalization of [UVIO2]2+ that do not involve reduction, mainly with Group 1 cations, are also covered, along with new advances in the photochemistry of the uranyl(VI) ion that involve the transient formation of formally uranyl(V) [UVO2]+ ion.

Ab initio molecular dynamics studies of hydroxide coordination of alkaline earth metals and uranyl.

Ab initio molecular dynamics (AIMD) simulations of the Mg2+, Ca2+, Sr2+ and UO22+ ions in either a pure aqueous environment or an environment containing two hydroxide ions have been carried out at the density functional level of theory, employing the generalised gradient approximation via the PBE exchange-correlation functional. Calculated mean M-O bond lengths in the first solvation shell of the aquo systems compared very well to existing experimental and computational literature, with bond lengths well within values measured previously and coordination numbers in line with previously calculated values. When applied to systems containing additional hydroxide ions, the methodology revealed increased bond lengths in all systems. Proton transfer events (PTEs) were recorded and were found to be most prevalent in the strontium hydroxide systems, likely due to the low charge density of the ion and the consequent lack of hydroxide coordination. For all alkaline earths, intrashell PTEs which occurred outside of the first solvation shell were most prevalent. Only three PTEs were identified in the entire simulation data of the uranium dihydroxide system, indicating the clear impact of the increased charge density of the hexavalent uranium ion on the strength of metal-oxygen bonds in aqueous solution. Broadly, systems containing more charge dense ions were found to exhibit fewer PTEs than those containing ions of lower charge density.

The use of columns of the zeolite clinoptilolite in the remediation of aqueous nuclear waste streams.

Mud Hills clinoptilolite has been used in an effluent treatment plant (SIXEP) at the Sellafield nuclear reprocessing site. This material has been used to remove 134/137Cs and 90Sr successfully from effluents for 3 decades. Samples of the zeolite have been tested in column experiments to determine their ability to remove radioactive Cs+ and Sr2+ ions under increasing concentrations of competing ions, Ca2+, Mg2+, Na+ and K+. These ions caused increased elution of Cs+ and Sr2+. Ca2+, Mg2+ and K+ were more effective competitors than Na+. For Na+, it was found that if concentration was reduced, then column performance recovered rapidly.

Robust artificial neural network for reliability and sensitivity analyses of complex non-linear systems.

Artificial Neural Networks (ANNs) are commonly used in place of expensive models to reduce the computational burden required for uncertainty quantification, reliability and sensitivity analyses. ANN with selected architecture is trained with the back-propagation algorithm from few data representatives of the input/output relationship of the underlying model of interest. However, different performing ANNs might be obtained with the same training data as a result of the random initialization of the weight parameters in each of the network, leading to an uncertainty in selecting the best performing ANN. On the other hand, using cross-validation to select the best performing ANN based on the ANN with the highest R2 value can lead to biassing in the prediction. This is as a result of the fact that the use of R2 cannot determine if the prediction made by ANN is biased. Additionally, R2 does not indicate if a model is adequate, as it is possible to have a low R2 for a good model and a high R2 for a bad model. Hence, in this paper, we propose an approach to improve the robustness of a prediction made by ANN. The approach is based on a systematic combination of identical trained ANNs, by coupling the Bayesian framework and model averaging. Additionally, the uncertainties of the robust prediction derived from the approach are quantified in terms of confidence intervals. To demonstrate the applicability of the proposed approach, two synthetic numerical examples are presented. Finally, the proposed approach is used to perform a reliability and sensitivity analyses on a process simulation model of a UK nuclear effluent treatment plant developed by National Nuclear Laboratory (NNL) and treated in this study as a black-box employing a set of training data as a test case. This model has been extensively validated against plant and experimental data and used to support the UK effluent discharge strategy.

Human Meibum Age, Lipid-Lipid Interactions and Lipid Saturation in Meibum from Infants.

Tear stability decreases with increasing age and the same signs of instability are exacerbated with dry eye. Meibum lipid compositional changes with age provide insights into the biomolecules responsible for tear film instability. Meibum was collected from 69 normal donors ranging in age from 0.6 to 68 years of age. Infrared spectroscopy was used to measure meibum lipid phase transition parameters. Nuclear magnetic resonance spectroscopy was used to measure lipid saturation. Increasing human meibum lipid hydrocarbon chain unsaturation with age was related to a decrease in hydrocarbon chain order, cooperativity, and in the phase transition temperature. The change in these parameters was most dramatic between 1 and 20 years of age. Meibum was catalytically saturated to determine the effect of saturation on meibum lipid phase transition parameters. Hydrocarbon chain saturation was directly related to lipid order, phase transition temperature, cooperativity, changes in enthalpy and entropy, and could account for the changes in the lipid phase transition parameters observed with age. Unsaturation could contribute to decreased tear film stability with age.

Ionic adsorption on the brucite (0001) surface: A periodic electrostatic embedded cluster method study.

Density functional theory (DFT) at the generalised gradient approximation level is employed within the periodic electrostatic embedded cluster method (PEECM) to model the brucite (0001) surface. Three representative studies are then used to demonstrate the reliability of the PEECM for the description of the interactions of various ionic species with the layered Mg(OH)2 structure, and its performance is compared with periodic DFT, an approach known to be challenging for the adsorption of charged species. The adsorption energies of a series of s block cations, including Sr2+ and Cs+ which are known to coexist with brucite in nuclear waste storage ponds, are well described by the embedded cluster model, provided that basis sets of triple-zeta quality are employed for the adsorbates. The substitution energies of Ca2+ and Sr2+ into brucite obtained with the PEECM are very similar to periodic DFT results, and comparison of the approaches indicates that two brucite layers in the quantum mechanical part of the PEECM are sufficient to describe the substitution. Finally, a detailed comparison of the periodic and PEECM DFT approaches to the energetic and geometric properties of differently coordinated Sr[(OH)2(H2O)4] complexes on brucite shows an excellent agreement in adsorption energies, Sr-O distances, and bond critical point electron densities (obtained via the quantum theory of atoms-in-molecules), demonstrating that the PEECM can be a useful alternative to periodic DFT in these situations.

Topological Study of Bonding in Aquo and Bis(triazinyl)pyridine Complexes of Trivalent Lanthanides and Actinides: Does Covalency Imply Stability?

The geometrical and electronic structures of Ln[(H2O)9]3+ and [Ln(BTP)3]3+, where Ln = Ce-Lu, have been evaluated at the density functional level of theory using three related exchange-correlation (xc-)functionals. The BHLYP xc-functional was found to be most accurate, and this, along with the B3LYP functional, was used as the basis for topological studies of the electron density via the quantum theory of atoms in molecules (QTAIM). This analysis revealed that, for both sets of complexes, bonding was almost identical across the Ln series and was dominated by ionic interactions. Geometrical and electronic structures of actinide (An = Am, Cm) analogues were evaluated, and [An(H2O)9]3+ + [Ln(BTP)3]3+ → [Ln(H2O)9]3+ + [An(BTP)3]3+ exchange reaction energies were evaluated, revealing Eu ↔ Am and Gd ↔ Cm reactions to favor the An species. Detailed QTAIM analysis of Eu, Gd, Am, and Cm complexes revealed increased covalent character in M-O and M-N bonds when M = An, with this increase being more pronounced in the BTP complexes. This therefore implies a small electronic contribution to An-N bond stability and the experimentally observed selectivity of the BTP ligand for Am and Cm over lanthanides.

The geometric structures, vibrational frequencies and redox properties of the actinyl coordination complexes ([AnO2(L)n](m); An = U, Pu, Np; L = H2O, Cl-, CO3(2-), CH3CO2(-), OH-) in aqueous solution, studied by density functional theory methods.

The geometric and electronic structures of the aqua, chloro, acetato, hydroxo and carbonato complexes of U, Np and Pu in both their (VI) and (V) oxidation states, and in an aqueous environment, have been studied using density functional theory methods. We have obtained micro-solvated structures derived from molecular dynamics simulations and included the bulk solvent using a continuum model. We find that two different hydrogen bonding patterns involving the axial actinyl oxygen atoms are sometimes possible, and may give rise to different An-O bond lengths and vibrational frequencies. These alternative structures are reflected in the experimental An-O bond lengths of the aqua and carbonato complexes. The variation of the redox potential of the uranyl complexes with the different ligands has been studied using both BP86 and B3LYP functionals. The relative values for the four uranium complexes having anionic ligands are in surprisingly good agreement with experiment, although the absolute values are in error by approximately 1 eV. The absolute error for the aqua species is much less, leading to an incorrect order of the redox potentials of the aqua and chloro species.

Which density functional should be used to study actinyl complexes?

The new M06 functional of Truhlar and co-workers is found to be competitive with high level ab initio methods in the study of the water exchange mechanism of the [UO(2)(OH(2))(5)](2+) ion, and of the redox potentials of the aqua complexes of [AnO(2)](2+) (An = U, Np and Pu).