Dynamic fracture: an example of convergence towards a discontinuous quasistatic solution

Considering a one-dimensional problem of debonding of a thin film in the context of Griffith’s theory, we show that the dynamical solution converges, when the speed of loading goes down to 0, to a quasistatic solution including an unstable phase of propagation. In particular, the jump of the debonding induced by this instability is governed by a principle of conservation of the total quasistatic energy, the kinetic energy being negligible.      

Using a Functional Model to Develop a Mathematical Formula

The unifying theme of models was incorporated into a required Science Capstone course for pre‐service elementary teachers based on national standards in science and mathematics. A model of a teeter‐totter was selectedfor use as an example of a functional model for gathering data as well as a visual model of a mathematical equation for developing the mathematical relationship for a Class 1 lever, M1D1=M1D1. In this study, 20 student groups (n=72) collected data using the model in an inquiry‐based activity. All groups developed the qualitative relationship, 13 groups developed a correct mathematical formula, 6 groups developed one‐half of the relationship (X = mass × distance), and 1 group attempted to develop a procedural relationship. The pre‐service elementary teachers used a variety of model types in the activity including visual/pictorial, functional/physical and mathematical‐both graphs and formulas. The use of the teeter‐totter model as a visual and functional model of a mathematical formula was a factor in developing the mathematical relationship.     

Improved Interpretation of Mercury Intrusion and Soil Water Retention Percolation Characteristics by Inverse Modelling and Void Cluster Analysis

This work addresses two continuing fallacies in the interpretation of percolation characteristics of porous solids. The first is that the first derivative (slope) of the intrusion characteristic of the non-wetting fluid or drainage characteristic of the wetting fluid corresponds to the void size distribution, and the second is that the sizes of all voids can be measured. The fallacies are illustrated with the aid of the PoreXpert^® inverse modelling package. A new void analysis method is then described, which is an add-on to the inverse modelling package and addresses the second fallacy. It is applied to three widely contrasting and challenging porous media. The first comprises two fine-grain graphites for use in the next-generation nuclear reactors. Their larger void sizes were measured by mercury intrusion, and the smallest by using a grand canonical Monte Carlo interpretation of surface area measurement down to nanometre scale. The second application is to the mercury intrusion of a series of mixtures of ground calcium carbonate with powdered microporous calcium carbonate known as functionalised calcium carbonate (FCC). The third is the water retention/drainage characteristic of a soil sample which undergoes naturally occurring hydrophilic/hydrophobic transitions. The first-derivative approximation is shown to be reasonable in the interpretation of the mercury intrusion porosimetry of the two graphites, which differ only at low mercury intrusion pressures, but false for FCC and the transiently hydrophobic soil. The findings are supported by other experimental characterisations, in particular electron and atomic force microscopy.     

Poly[nickel(II)‐di‐μ‐4,4′‐bipyridyl‐κ4N:N′‐μ‐dichromato‐κ2O:O′] and poly[copper(II)‐di‐μ‐4,4'‐bipyridyl‐κ4N:N′‐μ‐dichromato‐κ2O:O′]

The novel title hybrid isomorphous organic–inorganic mixed‐metal dichromates, [Ni(Cr₂O₇)(C₁₀H₈N₂)₂] and [Cu(Cr₂O₇)(C₁₀H₈N₂)₂], have been synthesized. A non‐centrosymmetric three‐dimensional (4,6)‐net is formed from a linear chain of vertex‐linked [Cr₂O]²⁻ and [MN₄O]²⁺ (M = Ni and Cu) units, which in turn are linked by the planar bidentate 4,4′‐­bipyridine ligand through the four remaining vertices of the [MN₄O]²⁺ octahedra. There are two such three‐dimensional nets that interpenetrate with inversion symmetry.     

Metabolically Active,Fully Hydrolysable Polymersomes

The synthesis and aqueous self‐assembly of a new class of amphiphilic aliphatic polyesters are presented. These AB block polyesters comprise polycaprolactone (hydrophobe) and an alternating polyester from succinic acid and an ether‐substituted epoxide (hydrophile). They self‐assemble into biodegradable polymersomes capable of entering cells. Their degradation products are bioactive, giving rise to differentiated cellular responses inducing stromal cell proliferation and macrophage apoptosis. Both effects emerge only when the copolymers enter cells as polymersomes and their magnitudes are size dependent.     

Perquinolines A–C: Unprecedented Bacterial Tetrahydroisoquinolines Involving an Intriguing Biosynthesis

Metabolic profiling of Streptomyces sp. IB2014/016‐6 led to the identification of three new tetrahydroisoquinoline natural products, perquinolines A–C ( 1 – 3 ). Labelled precursor feeding studies and the cloning of the pqr biosynthetic gene cluster revealed that 1 – 3 are assembled by the action of several unusual enzymes. The biosynthesis starts with the condensation of succinyl‐CoA and l ‐phenylalanine catalyzed by the amino‐7‐oxononanoate synthase‐like enzyme PqrA, representing rare chemistry in natural product assembly. The second condensation and cyclization events are conducted by PqrG, an enzyme resembling an acyl‐CoA ligase. Last, ATP‐grasp RimK‐type ligase PqrI completes the biosynthesis by transferring a γ‐aminobutyric acid or β‐alanine moiety. The discovered pathway represents a new route for assembling the tetrahydroisoquinoline cores of natural products.     

Successful management of discovered pH dependence in vancomycin recovery studies: novel HPLC method for microdialysis and plasma samples

Vancomycin is a glycopeptide antibiotic approved for the treatment of serious infections or patients allergic to beta-lactams. A rapid HPLC assay using UV detection for the determination in microdialysate and human plasma was developed. After sample preparation, using methanol and trichloroacetic acid for plasma and water for microdialysate, 20 microL were injected and separated on a RP(18) column. Overall, the assay exhibited good precision and accuracy. The diffusion properties of vancomycin investigated in in vitro microdialysis experiments revealed an unfavourable concentration dependence avertable by keeping a constant pH using phosphate buffer as perfusate. The mean relative recoveries were 27.8% [coefficient of variation (CV) 11.1%] and 33.2% (CV 8.3%) for retrodialysis and recovery experiments, respectively. Following characterization of vancomycin in in vitro microdialysis, the developed setting is suitable for application in (pre-)clinical studies.     

MOCVD-derived highly transparent, conductive zinc- and tin-doped indium oxide thin films: precursor synthesis, metastable phase film growth and characterization, and application as anodes in polymer light-emitting diodes

Four diamine adducts of bis(hexafluoroacetylacetonato)zinc [Zn(hfa)(2).(diamine)] can be synthesized in a single-step reaction. Single crystal X-ray diffraction studies reveal monomeric, six-coordinate structures. The thermal stabilities and vapor phase transport properties of these new complexes are considerably greater than those of conventional solid zinc metal-organic chemical vapor deposition (MOCVD) precursors. One of the complexes in the series, bis(1,1,1,5,5,5-hexafluoro-2,4-pentadionato)(N,N'-diethylethylenediamine)zinc, is particularly effective in the growth of thin films of the transparent conducting oxide Zn-In-Sn-O (ZITO) because of its superior volatility and low melting point of 64 degrees C. ZITO thin films with In contents ranging from 40 to 70 cation % (a metastable phase) were grown by low-pressure MOCVD. These films exhibit conductivity as high as 2900 S/cm and optical transparency comparable to or greater than that of commercial Sn-doped indium oxide (ITO) films. ZITO films with the nominal composition of ZnIn(2.0)Sn(1.5)O(z)() were used in fabrication of polymer light-emitting diodes. These devices exhibit light outputs and current efficiencies almost 70% greater than those of ITO-based control devices.     

Synthesis and magnetic properties comparison of M-Cu(II) and M-VO(II) Schiff base-porphyrazine complexes: what is the mechanism for spin-coupling?

Dimetallic Schiff base-porphyrazine (pz) compounds, denoted 1[M(1); M(2); R], have been prepared, where metal ion M(1) is incorporated into the pz core, and metal ion M(2) is bound to a bis(5-tert-butylsalicylidenimine) chelate built onto two amino nitrogens attached to the pz periphery; R is a solubilizing group (either propyl (Pr) or 3,4,5-trimethoxyphenyl (TMP)) attached to the remaining carbons of the pz periphery. The synthesis of 1[Cu; Cu; R], 1[Cu; VO; R], 1[ClMn; Cu; Pr], and 1[ClMn; VO; Pr] is discussed, the crystal structures of 1[Cu; Cu; TMP] and 1[ClMn; VO; Pr] are presented, and the magnetic properties of these compounds are compared. The pattern of ligand-mediated exchange coupling in these complexes is startling: for the Cu-M(2) complexes 1[Cu; VO; R] and 1[Cu; Cu; R], 2 x 10(2) < or = |J(Cu-VO)/J(Cu-Cu)|; for the ClMn-M(2) complexes 1[ClMn; Cu; Pr] and 1[ClMn; VO; Pr], J(ClMn-VO)/J(ClMn-Cu) approximately 1/3, an inverse ratio from that of the Cu-M(2) complexes, but with lesser discrimination. This coupling pattern is explained in terms of a novel orientation relative to the M(1)-M(2) direction: the "square-planar" Schiff base ligand set of M(2) is rotated in-plane by 45 degrees relative to the effectively coplanar pz ligand set of M(1).