Effect of substrate temperature on gold-catalyzed silicon nanostructures growth by hot-wire chemical vapor deposition (HWCVD)

The effect of substrate temperature on the structural property of the silicon nanostructures deposited on gold-coated crystal silicon substrate by hot-wire chemical vapor deposition (HWCVD) was studied. The uniformity and size of the as-grown silicon nanostructures is highly influenced by the substrate temperature. XRD, Raman and HRTEM measurements show the silicon nanostructures consist of small crystallites embedded within amorphous matrix. The crystallite size of the as-grown silicon nanostructures decreases with increases in substrate temperature. FTIR shows that these silicon nanostructures are highly disordered for sample prepared at substrate temperature above 250 °C. The correlation of crystallinity and structure disorder of the silicon nanostructures growth at different substrate temperature was discussed.     

Pollaczek contour integrals for the fixed-cycle traffic-light queue

The fixed-cycle traffic-light (FCTL) queue is the standard model for intersections with static signaling, where vehicles arrive, form a queue and depart during cycles controlled by a traffic light. Classical analysis of the FCTL queue based on transform methods requires a computationally challenging step of finding the complex-valued roots of some characteristic equation. Building on the recent work of Oblakova et al. (Exact expected delay and distribution for the fixed-cycle traffic-light model and similar systems in explicit form, 2016), we obtain a contour-integral expression, reminiscent of Pollaczek integrals for bulk-service queues, for the probability generating function of the steady-state FCTL queue. We also show that similar contour integrals arise for generalizations of the FCTL queue introduced in Oblakova et al. (2016) that relax some of the classical assumptions. Our results allow us to compute the queue-length distribution and all its moments using algorithms that rely on contour integrals and avoid root-finding procedures.

     

Intramolecularly Stabilised Group 10 Metal Stannyl and Stannylene Complexes: Multi‐pathway Synthesis and Observation of Platinum‐to‐Tin Alkyl Transfer

Reaction of [PdClMe(P^N)₂] with SnCl₂ followed by Cl‐abstraction leads to apparent Pd?C bond activation, resulting in methylstannylene species trans‐[PdCl{(P^N)₂SnClMe}][BF₄] (P^N=diaryl phosphino‐N‐heterocycle). In contrast, reaction of Pt analogues with SnCl₂ leads to Pt?Cl bond activation, resulting in methylplatinum species trans‐[PtMe{(P^N)₂SnCl₂}][BF₄]. Over time, they isomerise to methylstannylene species, indicating that both kinetic and thermodynamic products can be isolated for Pt, whereas for Pd only methylstannylene complexes are isolated. Oxidative addition of RSnCl₃ (R=Me, Bu, Ph) to M⁰ precursors (M=Pd or Pt) in the presence of P^N ligands results in diphosphinostannylene pincer complexes trans‐[MCl{(P^N)₂SnCl(R)}][SnCl₄R], which are structurally similar to the products from SnCl₂ insertion. This showed that addition of RSnCl₃ to M⁰ results in formal Sn?Cl bond oxidative addition. A probable pathway of activation of the tin reagents and formation of different products is proposed and the relevancy of the findings for Pd and Pt catalysed processes that use SnCl₂ as a co‐catalyst is discussed.     

Application of retention modelling to the simulation of separation of organic anions in suppressed ion chromatography

The ion-exchange separation of organic anions of varying molecular mass has been demonstrated using ion chromatography with isocratic, gradient and multi-step eluent profiles on commercially available columns with UV detection. A retention model derived previously for inorganic ions and based solely on electrostatic interactions between the analytes and the stationary phase was applied. This model was found to accurately describe the observed elution of all the anions under isocratic, gradient and multi-step eluent conditions. Hydrophobic interactions, although likely to be present to varying degrees, did not limit the applicability of the ion-exchange retention model. Various instrumental configurations were investigated to overcome problems associated with the use of organic modifiers in the eluent which caused compatibility issues with the electrolytically derived, and subsequently suppressed, eluent. The preferred configuration allowed the organic modifier stream to bypass the eluent generator, followed by subsequent mixing before entering the injection valve and column. Accurate elution prediction was achieved even when using 5-step eluent profiles with errors in retention time generally being less than 1% relative standard deviation (RSD) and all being less than 5% RSD. Peak widths for linear gradient separations were also modelled and showed good agreement with experimentally determined values.     

Mixed gated/exhaustive service in a polling model with priorities

In this paper we consider a single-server polling system with switch-over times. We introduce a new service discipline, mixed gated/exhaustive service, that can be used for queues with two types of customers: high and low priority customers. At the beginning of a visit of the server to such a queue, a gate is set behind all customers. High priority customers receive priority in the sense that they are always served before any low priority customers. But high priority customers have a second advantage over low priority customers. Low priority customers are served according to the gated service discipline, i.e. only customers standing in front of the gate are served during this visit. In contrast, high priority customers arriving during the visit period of the queue are allowed to pass the gate and all low priority customers before the gate. We study the cycle time distribution, the waiting time distributions for each customer type, the joint queue length distribution of all priority classes at all queues at polling epochs, and the steady-state marginal queue length distributions for each customer type. Through numerical examples we illustrate that the mixed gated/exhaustive service discipline can significantly decrease waiting times of high priority jobs. In many cases there is a minimal negative impact on the waiting times of low priority customers but, remarkably, it turns out that in polling systems with larger switch-over times there can be even a positive impact on the waiting times of low priority customers.     

Temporal Diffusion: From Microscopic Dynamics to Generalised Fokker–Planck and Fractional Equations

The temporal Fokker–Planck equation (Boon et al. in J Stat Phys 3/4: 527, 2003) or propagation–dispersion equation was derived to describe diffusive processes with temporal dispersion rather than spatial dispersion as in classical diffusion. We present two generalizations of the temporal Fokker–Planck equation for the first passage distribution function \(f_j(r,t)\) of a particle moving on a substrate with time delays \(\tau _j\). Both generalizations follow from the first visit recurrence relation. In the first case, the time delays depend on the local concentration, that is the time delay probability \(P_j\) is a functional of the particle distribution function and we show that when the functional dependence is of the power law type, \(P_j \propto f_j^{\nu - 1}\), the generalized Fokker–Planck equation exhibits a structure similar to that of the nonlinear spatial diffusion equation where the roles of space and time are reversed. In the second case, we consider the situation where the time delays are distributed according to a power law, \(P_j \propto \tau _j^{-1-\alpha }\) (with \(0< \alpha < 2\)), in which case we obtain a fractional propagation-dispersion equation which is the temporal analog of the fractional spatial diffusion equation (with space and time interchanged). The analysis shows how certain microscopic mechanisms can lead to non-Gaussian distributions and non-classical scaling exponents.     

Comparison of the Newtonian and relativistic predicted trajectories for a low-speed periodically delta-kicked system

The dynamics of a periodically delta-kicked Hamiltonian system moving at low speed (i.e., at speed much less than the speed of light) is studied numerically. In particular, the trajectory of the system predicted by Newtonian mechanics is compared with the trajectory predicted by special relativistic mechanics for the same parameters and initial conditions. We find that the Newtonian trajectory, although close to the relativistic trajectory for some time, eventually disagrees completely with the relativistic trajectory, regardless of the nature (chaotic, nonchaotic) of each trajectory. However, the agreement breaks down very fast if either the Newtonian or relativistic trajectory is chaotic, but very much slower if both the Newtonian and relativistic trajectories are nonchaotic. In the former chaotic case, the difference between the Newtonian and relativistic values for both position and momentum grows, on average, exponentially. In the latter nonchaotic case, the difference grows much slower, for example, linearly on average.     

Dual‐Targeting Dual‐Action Platinum(IV) Platform for Enhanced Anticancer Activity and Reduced Nephrotoxicity

A novel and highly efficient dual‐targeting platform was designed to ensure targeted in vivo delivery of dual‐action Pt^IV prodrugs. The dual targeting was established by liposomal encapsulation of Pt^IV complexes, thereby utilizing the enhanced permeability and retention (EPR) effect as the first stage of targeting to attain a high accumulation of the drug‐loaded liposomes in the tumor. After the release of the Pt^IV prodrug inside cancer cells, a second stage of targeting directed a portion of the Pt^IV prodrugs to the mitochondria. Upon intracellular reduction, these Pt^IV prodrugs released two bioactive molecules, acting both on the mitochondrial and on the nuclear DNA. Our Pt^IV system showed excellent activity in vitro and in vivo, characterized by a cytotoxicity in a low micromolar range and complete tumor remission, respectively. Notably, marked in vivo activity was accompanied by reduced kidney toxicity, highlighting the unique therapeutic potential of our novel dual‐targeting dual‐action platform.     

Ultrasound initiated miniemulsion polymerization of methacrylate monomers

The ultrasound initiated emulsion polymerization of methyl methacrylate (MMA), n-butyl methacrylate (BMA) and 2-ethylhexyl methacrylate (2EHMA) in the presence of sodium dodecylsulfate as a stabiliser produced latex particles in the size range of 70 nm to 110 nm with molecular weights of the order of 2-6 x 10(6) g mol(-1). The experimental data obtained show significant differences in the rates of polymerization of the methacrylate monomers in the order 2EHMA>BMA>MMA. The rate trend is discussed with respect to the physicochemical properties of the monomers. It is suggested from the results obtained that the mechanism involved in sonochemical formation of the latex particles is very similar to that of a conventional miniemulsion polymerization process.