Nanoscopic modelling of the adhesion, indentation and fracture characteristics of metallic systems via molecular dynamics simulations

Large-scale molecular dynamics simulations have been performed on canonical ensembles to model the adhesion and indentation characteristics of 3-D metallic nano-scale junctions in tip-substrate geometries, and the crack propagation in 2-D metallic lattices. It is shown that irreversible flows in nano-volumes of materials control the behaviour of the 3-D nano-contacts, and that local diffusional flow constitutes the atomistic mechanism underlying these plastic flows. These simulations show that the force of adhesion in metallic nano-contacts is reduced when adsorbate monolayers are present at the metal—metal junctions. Our results are in agreement with the conclusions of very accurate point-contact experiments carried out in this field. Our fracture simulations reveal that at low temperatures cleavage fractures can occur in both an elemental metal and an alloy. At elevated temperatures, the nucleation of dislocations is shown to cause a brittle-to-ductile transition. Limiting crack propagation velocities are computed for different strain rates and a dynamic instability is shown to control the crack movement beyond this limiting velocity, in line with the recent experimental results.

Structural and biological investigation of ferrocene-substituted 3-methylidene-1,3-dihydro-2H-indol-2-ones

The Knoevenagel condensation of 1,3-dihydro-2H-indol-2-one with ferrocene carboxaldehyde afforded an approximate 2:1 mixture of the geometrical isomers (E)- and (Z)-3-ferrocenylmethylidene-1,3-dihydro-2H-indol-2-one respectively in an overall 67% yield; the air and solution-stable isomers were readily separated by preparative thin layer chromatography and their structures were unequivocally elucidated in solution, by (1)H NMR spectroscopy, and in the solid phase, by X-ray crystallography; both isomers of displayed in vitro toxicity against B16 melanoma and Vero cell lines in the micromolar range and inhibited the kinase VEGFR-2 with IC(50) values of ca. 200 nM.

Numerical and experimental studies of a substructural identification strategy

For structural health monitoring it is impractical to identify a large structure with complete measurement due to limited number of sensors and difficulty in field instrumentation. Furthermore, it is not desirable to identify a large number of unknown parameters in a full system because of numerical difficulty in convergence. A novel substructural strategy was presented for identification of stiffness matrices and damage assessment with incomplete measurement. The substructural approach was employed to identify large systems in a divide-and-conquer manner. In addition, the concept of model condensation was invoked to avoid the need for complete measurement, and the recovery process to obtain the full set of parameters was formulated. The efficiency of the proposed method is demonstrated numerically through multi-storey shear buildings subjected to random force. A fairly large structural system with 50 DOFs was identified with good results, taking into consideration the effects of noisy signals and the limited number of sensors. Two variations of the method were applied, depending on whether the sensor could be repositioned. The proposed strategy was further substantiated experimentally using an eight-storey steel plane frame model subjected to shaker and impulse hammer excitations. Both numerical and experimental results have shown that the proposed substructural strategy gave reasonably accurate identification in terms of locating and quantifying structural damage.

Synthesis and enzymatic evaluation of the guanosine analogue 2-amino-6-mercapto-7-methylpurine ribonucleoside (MESG): insights into the phosphorolysis reaction mechanism based on the blueprint transition state: SN1 or SN2?

A modified experimental procedure for the synthesis of MESG (2-amino-6-mercapto-7-methylpurine ribonucleoside) 1 has been successfully performed and its full characterization is presented. High resolution ESI(+)-MSMS indicates both the nucleoside bond cleavage as the main fragmentation in the gas phase and a possible SN1 mechanism. Ab initio transition state calculations based on the blue print transition state support this mechanistic rationale and discard an alternative SN2 mechanism. Assays using purine nucleoside phosphorylase (PNP) enzyme (human and M. tuberculosis sources) indicate its efficiency in the phosphorolysis of MESG and allow the quantitative determination of inorganic phosphate in real time assay.