On the departure process of a leaky bucket system with long-range dependent input traffic

Due to the strong experimental evidence that the traffic to be offered to future broadband networks will display long-range dependence, it is important to study the possible implications that such traffic may have for the design and performance of these networks. In particular, an important question is whether the offered traffic preserves its long-range dependent nature after passing through a policing mechanism at the interface of the network. One of the proposed solutions for flow control in the context of the emerging ATM standard is the so-called leaky bucket scheme. In this paper we consider a leaky bucket system with long-range dependent input traffic. We adopt the following popular model for long-range dependent traffic: Time is discrete. At each unit time a random number of sessions is initiated, having the distribution of a Poisson random variable with mean λ. Each of these sessions has a random duration τ, where the integer random variable τ has finite mean, infinite variance, and a regularly varying tail, i.e., P(τ >К) ~ К^-Lα L(К), where 1 < α < 2 L(·) is a slowly varying function. Once a session is initiated, it generates one cell at each unit of time until its termination. We examine the departure process of the leaky bucket policing mechanism driven by such an arrival process, and show that it too is long-range dependent for any token buffer size and any - finite or infinite - cell buffer size. Moreover, upper and lower bounds for the covariance sequence of the output process are established. The above results demonstrate that long-range dependence cannot be removed by the kinds of flow control schemes that are currently being envisioned for broadband networks. This revised version was published online in June 2006 with corrections to the Cover Date.     

Asymmetric synthesis of 6-(2′,3′,4′,5′,6′-pentafluorophenyl)-δ-lactones via “allyl”boranes: application for the synthesis of fluorinated analog of key pharmacophore of statin drugs

Asymmetric “allyl”boration of pentafluorobenzaldehyde with various α-pinene based “allyl”boranes provides homoallylic alcohols in high de and ee; the alcohols have been converted into δ-lactones via acryloylation, ring-closing metathesis and hydrogenation. Pentafluorophenyl analog of key pharmacophore of statin drugs has been synthesized using diastereoselective epoxidation and regioselective reduction as key steps.     

Tuning size and catalytic activity of nano-clusters of cobalt oxide

Cobalt oxides were prepared by three different methods: (1) by reacting cobalt nitrate with oxalic acid, (2) co-precipitating cobalt nitrate with sodium carbonate, and (3) using sodium dodecyl sulphate as organic surfactant. All three samples were characterized before and after calcination by solvent extraction and the resulting products examined by IR spectroscopy. In the case of method 3, the removal of surfactant was followed by TGA studies. Products from all three methods were identified by XRD. Peaks in low angle XRD indicate the porous nature of the oxides. The morphology of the pores was studied by transmission electron microscopy. Some irregular pore structures were obtained for samples from methods 1 and 2, with an average size of 4–6 nm. Only the product from method 3 using SDS as template showed ordered structure and optimum size, and Brunauer-Emmet-Teller surface areas of the as-prepared, as well as the treated samples, exhibited H3 type hysteresis. The samples from the three methods were used as catalysts in the oxidation reaction of cyclohexane under mild conditions and the catalytic efficiency of the cobalt oxide was comparable with mesoporous cobalt oxides.     

Synthesis of homoallylic chiral tertiary alcohols via chelation-controlled diastereoselective nucleophilic addition on alpha-alkoxyketones: application for the synthesis of the C(1)-C(11) subunit of 8-epi-fostriecin

[reaction: see text] Chiral beta-syn-alkoxyhomoallylic alcohols derived from alkoxyallylboration of aldehydes upon oxidation provided the corresponding chiral ketones. Chelation-controlled nucleophilic addition to these ketones occurred in a highly stereoselective manner to afford anti-homoallylic tertiary alcohols. This methodology has been applied for the synthesis of the C(1)-C(11) subunit of C(8)-epi-fostriecin.     

Asymmetric allylboration of alpha,beta-enals as a surrogate for the enantioselective synthesis of allylic amines and alpha-amino acids

[reaction: see text] Optically pure allylic amines have been synthesized from alpha,beta-unsaturated aldehydes via allylboration with (-)-B-allyldiisopinocampheylborane, followed by Overman rearrangement. By incorporating crotyl and alkoxyallylboration, functionalization at delta-position was readily accomplished. By applying this methodology, the synthesis of several chiral alpha-amino acids has been achieved.     

Mild and Highly Efficient Protocol for the Synthesis of Benzimidazoles Using Samarium Triflate [Sm(OTf)3]

One-pot synthesis of benzimidazole compounds from ortho-phenylenediamine and a variety of aldehydes was developed under mild reaction conditions. All the reactions were carried out in the presence of samarium triflate (10 mol%) in acetonitrile at room temperature.     

Uncovering the Stoichiometry of Pyrococcus furiosus RNase P,a Multi‐Subunit Catalytic Ribonucleoprotein Complex,by Surface‐Induced Dissociation and Ion Mobility Mass Spectrometry

We demonstrate that surface‐induced dissociation (SID) coupled with ion mobility mass spectrometry (IM‐MS) is a powerful tool for determining the stoichiometry of a multi‐subunit ribonucleoprotein (RNP) complex assembled in a solution containing Mg²⁺. We investigated Pyrococcus furiosus (Pfu) RNase P, an archaeal RNP that catalyzes tRNA 5′ maturation. Previous step‐wise, Mg²⁺‐dependent reconstitutions of Pfu RNase P with its catalytic RNA subunit and two interacting protein cofactor pairs (RPP21⋅RPP29 and POP5⋅RPP30) revealed functional RNP intermediates en route to the RNase P enzyme, but provided no information on subunit stoichiometry. Our native MS studies with the proteins showed RPP21⋅RPP29 and (POP5⋅RPP30)₂ complexes, but indicated a 1:1 composition for all subunits when either one or both protein complexes bind the cognate RNA. These results highlight the utility of SID and IM‐MS in resolving conformational heterogeneity and yielding insights on RNP assembly.     

Synthesis,Characterization, DNA Binding Studies,Photocleavage, Cytotoxicity and Docking Studies of Ruthenium(II) Light Switch Complexes

A new ligand 3-(1H-imidazo[4,5-f][1,10]phenanthrolin-2yl)phenylboronic acid and its (IPPBA) three ruthenium(II) complexes [Ru(phen)₂(IPPBA)](ClO₄)₂ (1), [Ru(bpy)₂(IPPBA)](ClO₄)₂ (2) and [Ru(dmb)₂(IPPBA)](ClO₄)₂ (3) have been synthesized and characterized by elemental analysis, UV/VIS, IR, ¹H-NMR,¹³C-NMR and mass spectra. The binding behaviors of the three complexes to calf thymus DNA were investigated by absorption spectra, emission spectroscopy, viscosity measurements, thermal denaturation and photoactivated cleavage. The DNA-binding constants for complexes 1, 2 and 3 have been determined to be 7.9?×?10⁵ M^?1, 6.7?×?10⁵ M^?1 and 2.9?×?10⁵ M^?1. The results suggest that these complexes bound to double-stranded DNA in an intercalation mode. Upon irradiation at 365 nm, three ruthenium complexes were found to promote the cleavage of plasmid pBR322 DNA from super coiled form ? to nicked form ??. Further in the presence of Co²⁺, the emission of DNA–Ru(ΙΙ) complexes can be quenched. And when EDTA was added, the emission was recovered. The experimental results show that all three complexes exhibited the “on–off–on” properties of molecular “light switch”. The highest Cytotoxicity potential of the complex1 was observed on the Human alveolar adenocarcinoma (A549) cell line. Good agreement was generally found between the spectroscopic techniques and molecular docked model which provides further evidence of groove binding.     

The effects of mixture preburning on detonation wave propagation

Pressure gain combustion in the form of continuous detonations can provide a significant increase in the efficiency of a variety of propulsion and energy conversion devices. In this regard, rotating detonation engines (RDEs) that utilize an azimuthally-moving detonation wave in annular systems are increasingly seen as a viable approach to realizing pressure gain combustion. However, practical RDEs that employ non-premixed fuel and oxidizer injection need to minimize losses through a number of mechanisms, including turbulence-induced shock-front variations, incomplete fuel-air mixing, and premature deflagration. In this study, a canonical stratified detonation configuration is used to understand the impact of preburning on detonation efficiency. It was found that heat release ahead of the detonation wave leads to weaker shock fronts, delayed combustion of partially-oxidized fuel-air mixture, and non-compact heat release. Furthermore, large variations in wave speeds were observed, which is consistent with wave behavior in full-scale RDEs. Peak pressures in the compression region or near triple points were considerably lower than the theoretically-predicted values for ideal detonations. Analysis of the detonation structure indicates that this deflagration process is parasitic in nature, reducing the detonation efficiency but also leading to heat release far behind the wave that cannot directly strengthen the shock wave. This parasitic combustion leads to commensal combustion (heat release far downstream of the wave), indicating that it is the root cause of combustion efficiency losses.