Complex temporal patterns in molecular dynamics:a direct measure of the phase-space exploration by the trajectory at macroscopic time scales

Computer simulated trajectories of bulk water molecules form complex spatiotemporal structures at the picosecond time scale. This intrinsic complexity, which underlies the formation of molecular structures at longer time scales, has been quantified using a measure of statistical complexity. The method estimates the information contained in the molecular trajectory by detecting and quantifying temporal patterns present in the simulated data (velocity time series). Two types of temporal patterns are found. The first, defined by the short-time correlations corresponding to the velocity autocorrelation decay times (â‰0.1â€ps), remains asymptotically stable for time intervals longer than several tens of nanoseconds. The second is caused by previously unknown longer-time correlations (found at longer than the nanoseconds time scales) leading to a value of statistical complexity that slowly increases with time. A direct measure based on the notion of statistical complexity that describes how the trajectory explores the phase space and independent from the particular molecular signal used as the observed time series is introduced. © 2008 The American Physical Society.

Direct writing of fibre Bragg gratings by femtosecond laser

A method for inscribing fiber bragg gratings (FBG) using direct, point-by-point writing by an infrared femtosecond laser was described. The method requires neither phase-masks nor photosensitized fibers and hence offers remarkable technology flexibility. It requires a very short inscription time of less than 60 s per grating. Gratings of first to third order were produced in non-photosensitized, standard telecommunication fiber (SMF) and dispersion shifted fiber (DSF). The gratings produced in this method showed low insertion loss, narrow linewidth and strong, fundamental or high-order resonance.

Direct measurement of coherency limits for strain relaxation in heteroepitaxial core/shell nanowires

The growth of heteroepitaxially strained semiconductors at the nanoscale enables tailoring of material properties for enhanced device performance. For core/shell nanowires (NWs), theoretical predictions of the coherency limits and the implications they carry remain uncertain without proper identification of the mechanisms by which strains relax. We present here for the Ge/Si core/shell NW system the first experimental measurement of critical shell thickness for strain relaxation in a semiconductor NW heterostructure and the identification of the relaxation mechanisms. Axial and tangential strain relief is initiated by the formation of periodic a/2 〈110〉 perfect dislocations via nucleation and glide on {111} slip-planes. Glide of dislocation segments is directly confirmed by real-time in situ transmission electron microscope observations and by dislocation dynamics simulations. Further shell growth leads to roughening and grain formation which provides additional strain relief. As a consequence of core/shell strain sharing in NWs, a 16 nm radius Ge NW with a 3 nm Si shell is shown to accommodate 3% coherent strain at equilibrium, a factor of 3 increase over the 1 nm equilibrium critical thickness for planar Si/Ge heteroepitaxial growth. © 2012 American Chemical Society.

Bit-error probability for direct detection of optical RZ signal degraded by ASE noise and timing jitter

We analyze theoretically the interplay between optical return-to-zero signal degradation due to timing jitter and additive amplified-spontaneous-emission noise. The impact of these two factors on the performance of a square-law direct detection receiver is also investigated. We derive an analytical expression for the bit-error probability and quantitatively determine the conditions when the contributions of the effects of timing jitter and additive noise to the bit error rate can be treated separately. The analysis of patterning effects is also presented. © 2007 IEEE.

Direct observation of R...R distances in rare-earth (R) phosphate glasses by magnetic difference neutron diffraction

A magnetic difference neutron diffraction study of a rare-earth (Tb) phosphate glass has revealed exclusively the Tb...Tb distances. The difference between data taken with and without an applied magnetic field of 4 T shows Tb...Tb pairwise atomic correlations at 3.9 and 6.4 A, respectively, with relative coordination numbers of 1:14. The first distance arises when two Tb3+ ions share a common oxygen neighbor, and indicates a clustering of rare-earth ions. The second distance arises when two Tb3+ ions are coordinated to different oxygens in the same PO4 group, in a near-linear arrangement.

Site-selective direct arylation of unprotected adenine nucleosides mediated by palladium and copper:insights into the reaction mechanism

Reaction conditions facilitating the site-selective direct aryl functionalisation at the C-8 position of adenine nucleosides have been identified. Many different aromatic components may be effectively cross-coupled to provide a diverse array of arylated adenine nucleoside products without the need for ribose or adenine protecting groups. The optimal palladium catalyst loading lies between 0.5 and 5 mol %. Addition of excess mercury to the reaction had a negligible affect on catalysis, suggesting the involvement of a homogeneous catalytic species. A study by transmission electron microscopy (TEM) shows that metal containing nanoparticles, ca. 3 nm with good uniformity, are formed during the latter stages of the reaction. Stabilised PVP palladium colloids (PVP=N-polyvinylpyrrolidone) are catalytically active in the direct arylation process, releasing homogenous palladium into solution. The effect of various substituted 2-pyridine ligand additives has been investigated. A mechanism for the site-selective arylation of adenosine is proposed. © 2008 Elsevier Ltd. All rights reserved.

Direct observation of extremely low temperature catalytic dehydrochlorination of 1,1,1-trichloroethane over platinum

Fast X-ray photoelectron spectroscopy reveals that the efficient catalytic destruction of 1,1,1-trichloroethane occurs over Pt{111} surfaces at temperatures as low as 150 K. Decomposition occurs via rapid, sequential C-Cl bond scission to form an alkylidyne surface intermediate that in turn dehydrogenates above room temperature. Atomic chlorine liberated during dehydrochlorination undergoes efficient reaction with surface hydrogen, resulting in the evolution of gaseous HCl and small amounts of ethane, presumably via ethylidyne hydrogenation. Irreversible dehydrogenation of residual hydrocarbon fragments results in significant surface coking above 500 K.

Direct design of high channel-count fiber Bragg grating filters with low index modulation

A novel method for designing high channel-count fiber Bragg gratings (FBGs) is proposed. For the first time, tailored group delay is introduced into the target reflection spectra to obtain a more even distribution of the refractive index modulation. This approach results in the reduction of the maximum refractive index modulation to physically realizable levels. The maximum index modulation reduction factors are all greater than 5.5. This is a significant improvement compared with previously reported results. Numerical results show that the thus designed high channel-count FBG filters exhibit superior characteristics including 30 dB channel isolation, a flat-top and near 100% reflectivity in each channel. © 2012 Optical Society of America.

Direct observation of morphological development during the spin-coating of polystyrene-poly(methyl methacrylate) polymer blends

We present results of the direct observation, in real-space, of the phase separation of high molecular weight polystyrene and poly(methyl methacrylate) from ortho-xylene using our newly developed technique of high speed stroboscopic interference microscopy. Taking a fixed concentration (3 wt % in o-xylene) at a fixed composition (1:4 by weight) and by varying the rotational rate during the spin-coating process, we are able to observe the formation of a range of phase separated bicontinuous morphologies of differing length-scales. Importantly, we are able to show that the mechanism by which the final phase separated structure is formed is through domain coarsening when rich in solvent, before vitrification occurs and fixes the phase separated structure. The ability to directly observe morphological development offers a route toward controlling the length-scale of the final morphology through process control and in situ feedback, from a single stock solution. © 2013 Wiley Periodicals, Inc.

Direct activation of microcrystalline zeolites

In this work a direct activation route of zeolites is assessed. It consists of NH4-exchanging the as-synthesized solids before removing the organic template. Calcination afterwards serves to combust the organic template and creates the Brønsted sites directly; thus applying merely a single thermal step. This method simplifies their activation and the material suffers less thermal stress. The approach was particularly effective for microcrystalline beta and ferrierite zeolites. Thorough investigation of the template content and materials' texture points out to three relevant effects that can explain the effective exchange process: partial removal of the template during exchange creates substantial microporosity (ferrierite), the remaining template is reorganized within the pores (ferrierite) and finally, void space can exist due to the non-perfect matching between the network and template (beta). This shorter method appears suited for microcrystalline zeolites; it was ineffective for crystalline MFI types. © 2013 Elsevier B.V. All rights reserved.

The impact of foreign direct investment on labour productivity in the Chinese electronics industry

Foreign direct investment (FDI) may have a positive impact on labour productivity in recipient industries through direct introduction of capital, technology and management skills and indirectly through spillover effects on domestic firms. This study uses a model intended to examine the overall effects of inward FDI in the Chinese electronics industry. Official data are used for 41 sub-sectors of the industry in 1996 and 1997 having differing levels of FDI. Labour productivity is modelled as dependent on the degree of foreign presence in the industry and other variables, namely capital intensity, human capital and firm size for scale factors. The econometric results suggest that foreign presence in the industry is associated with higher labour productivity. © 2001 Elsevier Science Ltd.

The development and applications of the combined use of NMR and ultrasound

The objective of the research carried out in this report was to observe the first ever in-situ sonochemical reaction in the NMR Spectrometer in the megahertz region of ultrasound. Several reactions were investigated as potential systems for a sonochemical reaction followed by NMR spectroscopy. The primary problem to resolve when applying ultrasound to a chemical reaction is that of heating. Ultrasound causes the liquid to move and produces 'hot spots' resulting in an increase in sample temperature. The problem was confronted by producing a device that would counteract this effect and so remove the need to account for heating. However, the design of the device limited the length of time during which it would function. Longer reaction times were required to enable observations to be carried out in the NMR spectrometer. The fIrst and most obvious reactions attempted were those of the well-known ultrasonic dosimeter. Such a reaction would, theoretically, enable the author to simultaneously observe a reaction and determine the exact power entering the system for direct comparison of results. Unfortunately, in order to monitor the reactions in the NMR spectrometer the reactant concentrations had to be signifIcantly increased, which resulted in a notable increase in reaction time, making the experiment too lengthy to follow in the time allocated. The Diels-Alder Reaction is probably one of the most highly investigated reaction systems in the field of chemistry and it was this to which the author turned her attention. Previous authors have carried out ultrasonic investigations, with considerable success, for the reaction of anthracene with maleic anhydride. It was this reaction in particular that was next attempted. The first ever sonochemically enhanced reaction using a frequency of ultrasound in the megahertz (MHz) region was successfully carried out as bench experiments. Due to the complexity of the component reactants the product would precipitate from the solution and because the reaction could only be monitored by its formation, it was not possible to observe the reaction in the NMR spectrometer. The solvolysis of 2-chloro-2-methylpropane was examined in various solvent systems; the most suitable of which was determined to be aqueous 2-methylpropan-2-ol. The experiment was successfully enhanced by the application of ultrasound and monitored in-situ in the NMR spectrometer. The increase in product formation of an ultrasonic reaction over that of a traditional thermal reaction occurred. A range of 1.4 to 2.9 fold improvement was noted, dependent upon the reaction conditions investigated. An investigation into the effect of sonication upon a large biological molecule, in this case aqueous lysozyme, was carried out. An easily observed effect upon the sample was noted but no explanation for the observed effects could be established.

The use of lichen growth rings in lichenometry: some preliminary findings

Certain species of crustose lichens have concentrically zoned margins which probably represent yearly growth rings. These marginal growth rings offer an alternative method of studying annual growth fluctuations, establishing growth rate-size curves, and determining the age of thalli for certain crustose species. Hence, marginal growth rings represent a potentially valuable, unexploited, tool in lichenometry. In a preliminary study, we measured the widths of the successive marginal rings in 25 thalli of Ochrolechia parella (L.) Massal., growing at a maritime site in north Wales. Mean ring widths of all thalli varied from a minimum of 1.02 mm (the outermost ring) to a maximum of 2.06 mm (the third ring from the margin). There is some suggestion that marginal ring width and thallus size are positively correlated; and hence that growth rates increase in larger thalli in this small population. In a further study on recently exposed bedrock adjacent to Breidalon, SE Iceland, we examined the potential for using marginal growth rings to estimate thallus age of a lichen tentatively identified as a Rhizocarpon (possibly R. concentricum (Davies) Beltram.) and thus confirm the timing of surface exposure (c. 50 years). Collectively, these results suggest: 1) the measurement of marginal rings is a possible alternative method of studying the growth of crustose lichens; 2) O. parella may grow differently to other crustose species, exhibiting a rapidly increasing radial growth rate in thalli >40 mm; 3) where lichens with marginal rings grow on recently exposed surfaces (<60 yrs), minimum age estimates can be made using growth rings as an in situ indication of lichen growth rate; 4) it is suggested that this phenomenon could provide a valuable, previously unexploited, in situ lichenometric-dating tool in areas lacking calibration control.

Studies on the mechanism of action on antitumour imidazotetrazinones

The imidazotetrazinones are clinically active antitumour agents, temozolomide currently proving successful in the treatment of melanomas and gliomas. The exact nature of the biological processes underlying response are as yet unclear.This thesis attempts to identify the cellular targets important to the cytotoxicity of imidazotetrazinones, to elucidate the pathways by which this damage leads to cell death, and to identify mechanisms by which tumour cells may circumvent this action. The levels of the DNA repair enzymes O6-alkylguanine-DNA-alkyltransferase (O6-AGAT) and 3-methyladenine-DNA-glycosylase (3MAG) have been examined in a range of murine and human cell lines with differential sensitivity to temozolomide. All the cell lines were proficient in 3MAG despite there being 40-fold difference in sensitivity to temozolomide. This suggests that while 3-methyladenine is a major product of temozolomide alkylation of DNA it is unlikely to be a cytotoxic lesion. In contrast, there was a 20-fold variation in O6-AGAT levels and the concentration of this repair enzyme correlated with variations in cytotoxicity. Furthermore, depletion of this enzyme in a resistant, O6-AGAT proficient cell line (Raji), by pre-treatment with the free base O6-methylguanine resulted in 54% sensitisation to the effects of temozolomide. These observations have been extended to 3 glioma cell lines; results that support the view that the cytotoxicity of temozolomide is related to alkylation at the O6-position of guanine and that resistance to this drug is determined by efficient repair of this lesion. It is clear, however, the other factors may influence tumour response since temozolomide showed little differential activity towards 3 established solid murine tumours in vivo, despite different tumour O6-AGAT levels. Unlike mitozolomide, temozolomide is incapable of cross-linking DNA and a mechanism by which O6-methylguanine may exert lethality is unclear. The cytotoxicity of the methyl group may be due to its disruption of DNA-protein interactions, or alternatively cell death may not be a direct result of the alkyl group itself, but manifested by DNA single-strand breaks. Enhanced alkaline elution rates were found for the DNA of Raji cells treated with temozolomide following alkyltransferase depletion, suggesting a relationship between O6-methylguanine and the induction single-strand breaks. Such breaks can activate poly(ADP-ribose) synthetase (ADPRT) an enzyme capable of rapid and lethal depletion of cellular NAD levels. However, at concentrations of temozolomlde relevant in vivo little change in adenine nucleotides was detected in cell lines, although this enzyme would appear important in modulating DNA repair since inhibition of ADPRT potentiated temozolomide cytotoxicity in Raji cells but not O6-AGAT deficient GM892A cells. Cell lines have been reported that are O6-AGAT deficient yet resistant to methylating agents. Thus, resistance to temozolomide may arise not only by removal of the methyl group from the O6-position of guanine, but also from another mechanism involving caffeine-sensitive post-replication repair or mismatch repair activity. A modification of the standard Maxam Gilbert sequencing technique was used to determine the sequence specificity of guanine-N7 alkylation. Temozolomide preferentially alkylated runs of guanines with the intensity of reaction increasing with the number of adjacent guanines in the DNA sequence. Comparable results were obtained with a polymerase-stop assay, although neither technique elucidates the sequence specificity of O6-guanine alkylation. The importance of such specificity to cytotoxicity is uncertain, although guanine-rich sequences are common to the promoter regions of oncogenes. Expression of a plasmid reporter gene under the control of the Ha-ras proto~oncogene promoter was inhibited by alkylation with temozolomide when transfected into cancer cell lines, However, this inhibition did not appear to be related to O6~guanine alkylation and therefore would seem unimportant to the chemotherapeutic activity of temozolomide.

Coherence imaging by use of a Newton rings sampling function

We show that, with suitable optics in the arm of a Michelson interferometer, orthogonal galvo-scanning mirrors build a sampling function in the form of Newton rings when the two interferometer arms are matched. Using a low-coherence source, one can obtain transversal depth-resolved images. A fast display procedure using a storage oscilloscope was devised based on this method.