Positional Disorder Research Articles

Finite temperature phase transition in the two-dimensional Coulomb glass at low disorders

We present numerical evidence using Monte Carlo simulations of finite temperature phase transition in two dimensional Coulomb Glass lattice model with random site energies at half-filling. For the disorder strengths (W) studied in this paper, we find the existence of charge-ordered phase (COP) below the critical temperature (Tc(W)). Also, the probability distribution of staggered magnetization calculated at each W shows a two-peak structure at their respective critical temperature. Thus the phase transition from fluid to COP as a function of temperature is second order for all W. We find no evidence of a spin glass phase between a fluid and the COP. Further, we have used finite-size scaling analysis to calculate the critical exponents. The critical exponents at zero disorder are different from the one found at finite disorders, which indicates that the disorder is a relevant parameter here. The critical exponent for correlation length ν increases and Tc decreases with increasing disorder. Similar behaviour for ν was seen in the work of Overlin et al. for three dimensional Coulomb Glass model with a positional disorder. Our study also shows that other critical exponents are also a function of disorder.

CRYSTAL STRUCTURE AND HIRSHFELD SURFACE ANALYSIS OF (E)-5-PHENYL-3-((4-(TRIFLUOROMETHYL)BENZYLIDENE)AMINO)THIAZOLIDIN-2-IMINIUM BROMIDE

In the cation of the title salt, the central thiazolidine ring adopts an envelope conformation. In the crystal N-H ··· Br hydrogen bonds link the components into a bi-dimensional network with the cations and anions stacked parallel to plane (101). The molecular structure shows several positional disorders over -CF3 and thiazolidine fragments and these were modeled. The weak intermolecular interactions in the crystal structure are mainly constituted by H ··· F, H ·· · π and H ··· Br. Hirshfeld surface analysis were used to verify the contributions of the different intermolecular interactions.

Following the nucleation pathway from disordered liquid to gyroid mesophase.

Mesophases have order intermediate between liquids and crystals and arise in systems with frustration, such as surfactants, block copolymers, and Janus nanoparticles. The gyroid mesophase contains two interpenetrated, nonintersecting chiral networks that give it properties useful for photonics. It is challenging to nucleate a gyroid from the liquid. Elucidating the reaction coordinate for gyroid nucleation could assist in designing additives that facilitate the formation of the mesophase. However, the complexity of the gyroid structure and the extreme weakness of the first-order liquid to gyroid transition make this a challenging quest. Here, we investigate the pathway and transition states for the nucleation of a gyroid from the liquid in molecular simulations with a mesogenic binary mixture. We find that the gyroid nuclei at the transition states have a large degree of positional disorder and are not compact, consistent with the low surface free energy of the liquid-gyroid interface. A combination of bond-order parameters for the minor component is best to describe the passage from liquid to gyroid, among those we consider. The committor analyses, however, show that this best coordinate is not perfect and suggests that accounting for the relative ordering of the two interpenetrated networks in infant nuclei, as well as for signatures of ordering in the major component of the mesophase, would improve the accuracy of the reaction coordinate for gyroid formation and its use to evaluate nucleation barriers. To our knowledge, this study is the first to investigate the reaction coordinate and critical nuclei for the formation of any mesophase from an amorphous phase.

Collective lattice resonances in disordered and quasi-random all-dielectric metasurfaces

Collective lattice resonances in disordered 2D arrays of spherical Si nanoparticles (NPs) have been thoroughly studied within the framework of the coupled dipole approximation. Three types of defects have been analyzed: positional disorder, size disorder, and quasi-random disorder. We show that the positional disorder strongly suppresses either the electric dipole (ED) or the magnetic dipole (MD) coupling, depending on the axis along which the NPs are shifted. Contrarily, size disorder strongly affects only the MD response, while the ED resonance can be almost intact, depending on the lattice configuration. Finally, random removing of NPs from an ordered 2D lattice reveals a quite surprising result: hybridization of the ED and MD resonances with lattice modes remains observable even in the case of random removing of up to 84% of the NPs from the ordered array. The reported results could be important for rational design and utilization of metasurfaces, solar cells, and other all-dielectric photonic devices.

Synthesis and Atomic Structure of the Yb-Ga-Au 1/1 Quasicrystal Approximant.

The Yb-Ga-Au 1/1 quasicrystal approximant (AP) composition ranges from Yb14.0Ga20.6Au65.4 to Yb14.8Ga46.3Au38.9, and single crystals of the 1/1 AP having the composition Yb13.8Ga26.1Au60.1 were obtained by the self-flux technique. X-ray structural analysis demonstrated that the atomic structure [space group Im3; a = 14.6889(9) Å] can be described by the body-centered packing of Tsai-type rhombic triacontahedron (RTH) clusters. The positional disorder in these clusters, interpreted as the average of an orientationally disordered tetrahedron and triangle, results in positional disorder in the outer shells. The elemental distributions and positions of mixtures of Au and Ga atoms in the RTH clusters correspond to those in the isostructural Yb15Al36Au49 1/1 AP.

Effects of Disorder on Thermoelectric Properties of Semiconducting Polymers

Organic materials have attracted recent interest as thermoelectric (TE) converters due to their low cost and ease of fabrication. We examine the effects of disorder on the TE properties of semiconducting polymers based on the Gaussian disorder model (GDM) for site energies while employing Pauli’s master equation approach to model hopping between localized sites. Our model is in good agreement with experimental results and a useful tool to study hopping transport. We show that stronger overlap between sites can improve the electrical conductivity without adversely affecting the Seebeck coefficient. We find that positional disorder aids the formation of new conduction paths with an increased probability of carriers in high energy sites, leading to an increase in electrical conductivity while leaving the Seebeck unchanged. On the other hand, energetic disorder leads to increased energy gaps between sites, hindering transport. This adversely affects conductivity while only slightly increasing Seebeck and results in lower TE power factors. Furthermore, positional correlation primarily affects conductivity, while correlation in site energies has no effect on TE properties of polymers. Our results also show that the Lorenz number increases with Seebeck coefficient, largely deviating from the Sommerfeld value, in agreement with experiments and in contrast to band conductors. We conclude that reducing energetic disorder and positional correlation, while increasing positional disorder can lead to higher TE power factors.

Effect of Backbone, Sequence, and Positional Disorders on Electrical Transport in Modified Poly(dA)–Poly(dT) DNA Wire

The effect of medium and thermal fluctuations on charge transport in two types of modified poly(dA)–poly(dT) DNA was studied by calculating the transmission probability and current–voltage ( I–V ) characteristics of a model DNA wire sandwiched between two metal electrodes. Modification was performed by randomly replacing several A–T base pairs with C–G or G–C base pairs along the DNA chain. The medium–DNA interaction was modeled as the backbone onsite energy disorder in the DNA tight-binding Hamiltonian. The helicity of the molecule was considered by incorporating twist-angle-dependent intrastrand hopping amplitude in the model. Thermal fluctuation was modeled by varying the twist angles of each base in the DNA wire. Twist-angle disorder was influenced by temperature and frequency. The I–V results obtained by modeling the backbone disorder effect showed that the current decreased and the threshold voltage generally increased as disorder strength increased to a critical value. The current increased and the threshold voltage decreased as the disorder strength exceeded this critical value. However, certain values of the backbone disorder reduced the threshold voltage before the critical value was reached because the transmission bands shifted toward the Fermi energy. The results of thermal fluctuation modeling indicated that increasing thermal fluctuation (increasing temperature and decreasing frequency) degraded the electrical properties of the DNA modified with C–G base pairs but enhanced those of the DNA modified by G–C base pairs. This trend, however, did not always hold for all frequency values for the latter DNA type.

Investigation on two triphenylene based electron transport materials

Promoting electron mobility is the key to designing high performance electron transport materials (ETMs). Formation of intermolecular interaction can be helpful to enhance their electron mobilities as a result of more ordered molecular stacking. Here, to reveal the inherent influence of intermolecular π-π stacking on the electron mobilities, we designed two ETMs, namely, 2,4-diphenyl-6-[3-(2-triphenylenyl)phenyl]-1,3,5-triazine (TPTRZ) and 2,4-diphenyl-6-[4′-(2-triphenylenyl)[1,1′-biphenyl]-3-yl]-1,3,5-triazine (TPPTRZ). Thermal, photophysical and electrochemical measurement results indicate they are good ETM candidates. Additionally, TPTRZ and TPPTRZ exhibit high electron mobilities of 3.60×10−5 and 3.58×10−5 cm2 V−1 s−1, respectively, at an electric field of 7×105 V cm−1. By taking X-ray single crystal structure, theoretical calculation and time of flight (TOF) results into consideration, it is revealed that strong intermolecular π-π stacking induced by planar triphenylene and triphenyltriazine units renders TPTRZ and TPPTRZ small energetic and positional disorder parameters, and results in their high electron mobilities thereby. By further enhancing intermolecular π-π stacking, ETMs with even higher electron mobilities can thus be anticipated.

The Impact of Behaviour and Emotions of Children with Cerebral Palsy on their Skills of Daily Activities as well as their Parent`s Quality of Life

Reseach background. Cerebral palsy is a disorder of movement or position resulting from the immature encephalon defect or damage. Level of independence, behavioural and emotional skills of children with cerebral palsy are some of the main parameters of social development. Psychological factor is very important, too. Independent movement disorders and lack of professional help cause a lot of psychological problems in adolescence – depression, nervous excitement, at the time when they begin to understand that they are different from their peers. On the other hand, diffculties which they experience are not short-term, which can be overcome by mobilization of forces and the available internal resources, therefore child’s adequacy also highly depends on the parents’ quality of life. The goal of research was to evaluate behavioural and emotional impact on children’s with cerebral palsy skills of daily activities as well as their parents’ quality of life. Methods. The survey was conducted from May 2014 till April 2015 in Kaunas medical institutions which provided rehabilitation services for children. 30 children with cerebral palsy and their parents participated in the study. Average age of children who participated in the study did not differ signifcantly depending on gender and was 11.6 ± 2.1 years. Results. After the assessment of behavioural and emotional functions of children with cerebral palsy it became clear that they were the most successful in not talking back and swearing near adults. After the assessment of daily activity skills for children with cerebral palsy, it was obtained that the task which was performed the best by the children was communication, and the worst – cooking, bathing and taking the shower, as well as housework. Assessment of parents’ quality of life showed that the best evaluated by parents was their ability to perform what, in their opinion, was necessary in everyday activities, the worst – favourable physical environment for their health. Assessing the impact of behaviour and emotions on children’s with cerebral palsy skills of daily activities, statistically signifcant association was obtained (p < 0.05) between the scales of emotional and behavioural functions and parents’ quality of life among children with cerebral palsy. The study did not show statistically signifcant difference between children’s gender, age, and form of the disease. Conclusions. Children’s with cerebral palsy behaviour and emotions had signifcant influence on their daily living skills (p < 0.005). Children’s with cerebral palsy behaviour and emotions were mostly connected to their ability to use the toilet; the least connection was related to preparation / dressing skills. Children’s with cerebral palsy behaviour and emotions had a signifcant influence on their parent’s quality of life (p < 0.005). Children’s with cerebral palsy behaviour and emotions affected their parent’s environment and health the most, and the least they affected parent’s negative emotions.Keywords: cerebral palsy, behaviour, emotions, quality of life.

A new descendant of the γ-brass family in the zinc rich Ni-Zn-In system

The first ternary intermetallic phase - Ni11.4+xZn19.8In14.9-y (0 ≤ x ≤ 0.2; 0 ≤ y ≤ 0.1) in the Ni-Zn-In system is presented. The structure of the phase has been analysed by single crystal X-ray diffraction. Due to the similar X-ray scattering factors for Ni and Zn, a combination of X-ray and neutron diffraction has been employed to identify accurate sites of Ni and Zn in the structure of the Ni-Zn-In phase. The phase is structurally complex and adopts a narrow homogeneity range. The structure crystallizes in the orthorhombic space group Cmcm (63) and contains 46 atoms per unit cell which bears all types of disorder phenomena (vacancies, mixed site occupancies, and positional disorders) that is typical for complex metallic alloys. The structure is mostly tetrahedrally close-packed and is generated mainly by two types of endohedral clusters: a 12-atom cluster that is closely related to an icosahedron and an 11-atom polyhedron that is related to twinned cuboctahedron. The phase is stabilized at valance electron concentration between 1.82 and 1.83 e/a.

Crystal structures of 1'-amino-cobaltocenium-1-carb-oxy-lic acid chloride monohydrate and of its azo dye 1'-[2-(1-amino-2,6-dimethylphenyl)diazen-1-yl]cobaltocenium-1-carb-oxy-lic acid hexa-fluorido-phosphate monohydrate.

1'-Amino-cobaltocenium-1-carb-oxy-lic acid chloride, [Co(C5H6N)(C6H5O2)]Cl·H2O, (3), and its azo derivative 1'-[2-(1-amino-2,6-dimethylphenyl)diazen-1-yl]cobaltocenium-1-carb-oxy-lic acid hexa-fluorido-phosphate, [Co(C13H14N3)(C6H5O2)]PF6·H2O (5) were obtained from cobaltocenium-1,1'-di-carb-oxy-lic acid hexa-fluorido-phosphate by converting one carboxyl group to its chloro-carboxyl derivative followed by chloride/azide exchange, Curtius rearrangement, diazo-tiation and azo coupling with 2,6-di-methyl-aniline. Both title compounds crystallize as their monohydrates. In the crystal structure of 3, both functional groups lie in the same direction, with the Cp rings being nearly eclipsed, and participate in an extended hydrogen-bonded supra-molecular network including the counter-ion and the water mol-ecule of crystallization. Although the functional groups in 5 are somewhat further apart, bearing a greater torsion angle with the Cp rings now staggered, a similar supra-molecular network is observed with not only the carb-oxy-lic acid and azo groups, but also with the more remote amino group participating in a hydrogen-bonded network, again including the counter-ion and the water mol-ecule. The hexa-fluorido-phosphate ion shows positional disorder. Compound 3 was refined as an inversion twin. In 5, each of the six F atoms is disordered over two sets of sites in a 1:1 ratio.

Disorder-Induced Phase Transitions in the Transmission of Dielectric Metasurfaces.

Light interaction with disordered materials is both complex and fascinating at the same time. Here, we reveal disorder-induced phase transitions in a dielectric Huygens' metasurface made from silicon nanocylinders that simultaneously support an electric and magnetic dipole resonance. Depending on the degree of positional disorder and the spectral detuning of the two resonances, the phase angle of the transmission coefficient exhibits a clear phase transition from normal to anomalous dispersion. Combined with the considerations of whether the resonances of spectrally detuned particles appear as separated or overlapping, we distinguish four different phase states. We study this phenomenon analytically by employing dipole particles and disclose the entire phase diagram, support our insights with full-wave simulations of actual structures, and corroborate the findings with experimental results. Unveiling this phenomenon is a milestone simultaneously in the growing fields of metamaterial-inspired silicon nanophotonics, photonics in disordered media, and the fundamental physics of phase transitions.

XAFS investigation of the correlation of Bi-sublattice disorder with ferromagnetism of multiferroic BiFeO3 nanoparticle

Practical utilization of room temperature multiferroic BiFeO3 is intrinsically limited by the absence of ferromagnetism. In this backdrop, development of weak ferromagnetism in 20 nm-sized BiFeO3 nanoparticles is very optimistic. The origin of ferromagnetism is curious and paradoxical from long-range-order perspective since average superexchange angle Fe–O–Fe of the nanoparticle is in antiferromagnetic configuration. In this work, we resolve this paradox by establishing the beneficial role of local disorder with x-ray absorption spectroscopy. We distinguish between the natures of (Bi, Fe)-sublattice disorder and establish their correlation that eventually leads to ferromagnetism. Our results reveal intrinsic large Bi positional disorder, which may be attributed to 6s2 lone pair activity of Bi atom and which leads to greater susceptibility of Bi-sublattice to modification during size reduction. Thus, local (BiO6, FeO6) units are observed to undergo large distortion and rotation respectively. We demonstrate with calculations that FeO6 rotation is geometric consequence of BiO6 distortion. In the case of our BiFeO3 nanoparticles, experimental BiO6 disorder induces FeO6 rotation that drives Fe–O–Fe into ferromagnetic configuration. These local ferromagnetic units give rise to weak magnetism. This structural route to magnetism in BiFeO3 can be generalized to encourage A-site disorder controlled magnetism or any functional octahedral rotation in ABO3 perovsites. The results additionally propagate the effectiveness of particle size-dependence in generating A-site strain rather than chemical doping or external pressure.

Crystal structures of two PCN pincer iridium complexes and one PCP pincer carbodi-phospho-rane iridium inter-mediate: substitution of one phosphine moiety of a carbodi-phospho-rane by an organic azide.

The structure of [Ir{(4-Cl-C6H4N3)C(dppm)-κ3 P,C,N}(dppm-κ2 P,P')]Cl·1.5CH2Cl2·0.5C7H8 (C57H48Cl2IrN3P4·1.5CH2Cl2·0.5C7H8) (2), dppm = bis-(di-phenyl-phosphino)methane {systematic name: [7-(4-chloro-phen-yl)-1,1,3,3-tetra-phenyl-5,6,7-tri-aza-κN 7-1,3λ4-diphospha-κP 1-hepta-4,6-dien-4-yl][methyl-ene-bis(di-phenyl-phosphine)-κ2 P,P']iridium(I) chloride-di-chloro-methane-toluene (2/3/1)}, resulting from the reaction of [IrClH{C(dppm)2-κ3 P,C,P)(MeCN)]Cl (1a) with 1-azido-4-chloro-benzene, shows a monocationic five-coordinate IrI complex with a distorted trigonal-bipyramidal geometry. In 2, the iridium centre is coordinated by the neutral triazeneyl-idene-phospho-rane (4-Cl-C6H4N3)C(dppm) acting as a PCN pincer ligand, and a chelating dppm unit. The structure of the coordination compound [IrCl(CN)H(C(dppm)2-κ3 P,C,P)]·CH3CN, (C52H45ClIrNP4·CH3CN) (1b) [systematic name: chlorido-cyanidohydrido(1,1,3,3,5,5,7,7-octa-phenyl-1,3λ5,5λ4,7-tetra-phospha-κ2 P 1,P 7-hept-3-en-4-yl)iridium(III) aceto-nitrile monosolvate], prepared from 1a and KCN, reveals an octa-hedral IrIII central atom with a meridional PCP pincer carbodi-phospho-rane (CDP) ligand; the chloride ligand is located trans to the central carbon of the CDP functionality while the hydrido and cyanido ligands are situated trans to each other. The chiral coordination compound [Ir(CN)((4-Cl-C6H4N3)CH(CH(P(Ph)2)2)-κ3 P,C,N)(dppm-κ2 P,P')]·2CH3OH, (C58H48ClIrN4P4·2CH3OH) (3) (systematic name: {4-[3-(4-chloro-phen-yl)triazenido-κN 3]-1,1,3,3-tetra-phenyl-1,3λ5-diphospha-κP 1-but-2-en-4-yl}cyanido[methyl-enebis(di-phenyl-phosphine)-κ2 P,P']iridium(III) methanol disolvate), formed via prolonged reaction of 1-azido-4-chloro-benzene with 1b, features a six-coordinate IrIII central atom. The iridium centre is coordinated by the dianionic facial PCN pincer ligand [(4-Cl-C6H4N3)CH(CH(P(Ph2)2)2)], a cyanido ligand trans to the central carbon of the PCN pincer ligand and a chelating dppm unit. Complex 2 exhibits a 2:1 positional disorder of the Cl- anion. The CH2Cl2 and C7H8 solvent mol-ecules show occupational disorder, with the toluene mol-ecule exhibiting additional 1:1 positional disorder with some nearly overlying carbon atoms.

Disorder Effect on the Transmission of Second Harmonic Waves in One-Dimensional Periodically Poled LiTaO<sub>3</sub>

One of the methods for calculating electromagnetic wave dispersion in multi-layer structures is the transfer matrix method. In this paper, we use the transfer matrix method for second harmonic generation in a nonlinear multilayer structure. The nonlinear photonic crystals investigated in this paper are as one-dimensional multi-layered structures including ferroelectric materials such as LiTaO3. Our goal is to investigate the effect of the disorder on the transmission spectrum of electromagnetic waves. Our results showed that positional disorder has different effects on the transmitting band and the gap band. The disorder in the transmitting band reduces the transmission coefficient of the waves and increases the transmission coefficient of the waves in the gap band. Such work has not yet been done on nonlinear photonic crystals producing the second harmonic.

DIAGNOSTIC VALUE OF STRUCTURAL AND FUNCTIONAL CHANGES IN THE CAROTID AND VERTEBRAL ARTERIES IN ARTERIAL HYPERTENSION, ASSOCIATED WITH BENIGN PAROXYSMAL POSITIONAL VERTIGO

Objective of the study was to assess the diagnostic significance of hemodynamic disorders in the area of carotid and vertebral arteries in patients with hypertension combined with benign paroxysmal positional vertigo (DPPG) using ultrasound duplex scanning of neck vessels. Material and methods . Thirty eight patients of the clinic of Federal Research Center for Fundamental and Translational Medicine with hypertension and concomitant dizziness were examined. The state of carotid and vertebral arteries, blood flow in the arteries were assessed by duplex ultrasound scanning using the Vivid E9 apparatus. Results and discussion. The influence of the blood flow at the level of carotid and vertebral arteries on the severity of clinical symptoms of dizziness in patients with hypertension with concomitant DPPG was shown. The clinical significance of atherosclerotic changes in carotid arteries, tortuosity of carotid and vertebral arteries of the effectiveness of treatment and prevention of dizziness in patients with hypertension and DPPG was revealed. It is shown that in patients with hypertension and comorbid DPP, the severity of the relationship of hemodynamically significant changes in the carotid and vertebral arteries with clinical manifestations of dizziness is greater than in patients with hypertension without DPP. The use of ultrasound duplex scanning of brachiocephalic arteries in hypertension with comorbid vertigo allows for differential diagnosis of benign paroxysmal positional vertigo and cerebrovascular dyscirculatory disorders, the degree of their participation in clinical manifestations of dizziness. A new medical technology for the diagnosis of pathogenic mechanisms of dizziness in patients with hypertension, using ultrasound duplex scanning of carotid and vertebral arteries, allows to personalize treatment and prevention in such patients.

All about that base: investigating the role of ligand basicity in pyridyl complexes derived from a copper-Schiff base coordination polymer.

The role of ligand basicity in complex formation has been investigated using monodentate pyridyls or benzimidazole (mP) in combination with a solution-stable species derived form a coordination polymer, [Cu(L)] (where L = 2-(2-hydroxybenzylidene-amino)phenol). The 12 [Cu(L)(mP)n] complexes generated, combined with the {[Cu(L)]2(pP)} complexes from our previous work (where pP is a polypyridyl ligand), allow us to gauge the likelihood of complex formation based on the pKa of the conjugate acid of the pyridyl ligands and Hammett parameter, σ. Above pKa ≈ 4.5, complexes are formed where the only ligands are L2- and mP or pP and the packing interactions are predominantly van der Waals. Below this value, complex formation is unlikely unless there are additional oxygen ligands in the Jahn-Teller axis of the Cu(ii) ion. The structures of two literature [Cu(L)(bP)] complexes, where bP is a chelating bidentate pyridyl ligand are also re-examined to resolve the positional disorder in the [Cu(L)] moiety.

Strong interactions and subradiance in disordered metamaterials

We provide detailed comparisons between experimental findings and numerical simulations of large cooperatively interacting, spatially disordered metamaterial arrays, consisting of asymmetrically split rings. Simulation methods fully incorporate strong field-mediated inter-meta-atom interactions between discrete resonators and statistical properties of disorder, while approximating the resonators' internal structure. Despite the large system size, we find a qualitative agreement between the simulations and experiments, and characterize the microscopic origins of the observed disorder response. Our microscopic description of macroscopic electrodynamics reveals how the response of disordered arrays with strong field-mediated interactions is inherently linked to their cooperative response to electromagnetic waves where the multiple scattering induces strong correlations between the excitations of individual resonators. Whereas for a regular array the response can be overwhelmingly dominated by a spatially-extended collective eigenmode with subradiant characteristics, a gradual increase of the positional disorder rapidly leads to a spatial localization of both the electric and magnetic dipolar excitation profile of this eigenmode. We show how the effects of disorder and cooperative interactions are mapped onto the transmission resonance in the far field spectrum and measure the "cooperative Lamb shift" of the resonance that is shifting toward the red as the disorder increases. The interplay between the disorder and interactions generally is most dramatic in the microwave arrays, but we find that in suitable regimes the strong disorder effects can be achieved also for plasmonic optical systems.

Improved Models for Metallic Nanoparticle Cores from Atomic Pair Distribution Function (PDF) Analysis

X-ray atomic pair distribution functions (PDFs) were collected from a range of canonical metallic nanomaterials, both elemental and alloyed, prepared using different synthesis methods and exhibiting drastically different morphological properties. Widely applied shape-tuned attenuated crystal (AC) fcc models proved inadequate, yielding structured, coherent, and correlated fit residuals. However, equally simple discrete cluster models could account for the largest amplitude features in these difference signals. A hypothesis testing based approach to nanoparticle structure modeling systematically ruled out effects from crystallite size, composition, shape, and surface faceting as primary factors contributing to the AC misfit. On the other hand, decahedrally twinned cluster cores were found to be the origin of the AC structure misfits for a majority of the nanomaterials reported here. It is further motivated that the PDF can readily differentiate between the arrangement of domains in these multiply twinned motifs. Most of the nanomaterials surveyed also fall within the sub-5 nm size regime where traditional electron microscopy cannot easily detect and quantify domain structures, with sampling representative of the average nanocrystal synthesized. The results demonstrate that PDF analysis is a powerful method for understanding internal atomic interfaces in small noble metallic nanomaterials. Such core cluster models, easily built algorithmically, should serve as starting structures for more advanced models able to capture atomic positional disorder, ligand induced or otherwise, near nanocrystal surfaces.

Newts can normalize duplicated proximal-distal disorder during limb regeneration.

Urodele animals can regenerate their limbs from the blastemas. The previous results of grafting proximal blastemas to distal limb levels (P to D transplantation) led to serial duplication of limb segments. However, it is unknown whether grafting to any distal levels in P to D transplantation causes serial duplication. In other words, it is unknown whether or not newt limbs can normalize such a kind of duplicated type of positional disorder in the proximal-distal axis. Therefore, we grafted the most proximal blastemas to various distal levels of the proximal-distal axis using newts (Pleurodeles waltl). The transgenic newts expressing green fluorescent protein or mCherry were used to clearly distinguish between donor and host tissues. Normal segmental formation without duplication occurred in P to D transplantation within the stylopod. In addition, donor blastemas lost the fates of the stylopods, and the missing portion in the stylopod by amputation was restored by the insertion of host cells. In contrast, the blastemas from the stylopod formed whole limbs after transplantation to the tail. These results showed that urodele limbs can normalize the duplicated type of positional disorder within the stylopod by erasing a part of the fate in the blastemas. Developmental Dynamics 247:1276-1285, 2018. © 2018 Wiley Periodicals, Inc.