Dynamic Scheduling of a Multiclass Fluid Model with Transient Overload

We study the optimal dynamic scheduling of different requests of service in a multiclass stochastic fluid model that is motivated by recent and emerging computing paradigms for Internet services and applications. In particular, our focus is on environments with specific performance guarantees for each class under a profit model in which revenues are gained when performance guarantees are satisfied and penalties are incurred otherwise. Within the context of the corresponding fluid model, we investigate the dynamic scheduling of different classes of service under conditions where the workload of certain classes may be overloaded for a transient period of time. Specifically, we consider the case with two fluid classes and a single server whose capacity can be shared arbitrarily among the two classes. We assume that the class 1 arrival rate varies with time and the class 1 fluid can more efficiently reduce the holding cost. Under these assumptions, we characterize the optimal server allocation policy that minimizes the holding cost in the fluid model when the arrival rate function for class 1 is known. Using the insights gained from this deterministic case, we study the stochastic fluid system when the arrival rate function for class 1 is random and develop various policies that are optimal or near optimal under various conditions. In particular, we consider two different types of heavy traffic regimes and prove that our proposed policies are strongly asymptotically optimal. Numerical examples are also provided to demonstrate further that these policies yield good results in terms of minimizing the expected holding cost.     

Synthesis and properties of poly(1-phenyl-1-octyne)s containing stereogenic and chromophoric pendant groups

Poly(1-phenyl-1-octyne)s containing different stereogenic and chromophoric pendants {-[(C6H13)C=C(C6H4-p-CO2-R)]n-R=[(1S)-endo]-(-)-borneyl (P3), (1R,2S,5R)-(-)-menthyl (P4),―C6H4-p-(1R,2S,5R)-(-)-menthyl (P5), 2-napthyl (P6), 4-biphenylyl (P7)} have been designed and synthesized. The polymers are prepared in moderate yields by WCl6-Ph4Sn and possess high molecular weights (Mw up to 64000). The structures and properties of the polymers are characterized and evaluated by NMR, TGA, UV, CD, PL, and EL analyses...     

EPR of Mn2+ doping unannealed single crystal of (La2O3)0.95(CeO2)0.05

X-band room temperature EPR spectra have been recorded for Mn²⁺ ion doping unannealed (La₂O₃)_0.95(CeO₂)_0.05 host crystal. The data are analysed using a rigorous least-squares fitting procedure in which a large number of lines characterized by ΔM = ± 1, Δm = 0 transition, obtained for several orientations of the static magnetic field, are simultaneously fitted. Combined with the knowledge of the absolute sign of the hyperfine interaction parameter. A, the hyperfine Hamiltonian parameters A, B, Q as reported in this paper, are given with their correct signs. The information on the linewidth is used to deduce the deviation of the crystal-field axes of different Mn²⁺ ions from the c axis; on the basis of the model proposed here these deviations are found to be between 0 and 10°.     

The hydration process of La2O3 studied by the electron spin resonance of Gd3+ and Mn2+ ions

The hydration of single-crystal La₂O₃ samples was studied following the evolution versus time of ESR spectra of Gd³⁺ and Mn²⁺ ions which enter the lattice substitutionally at lanthanum sites. Our results, which confirm those obtained previously on the macroscopic scale, permit a better understanding of the hydration process on the atomic scale.     

New aerobic oxidation of benzylic compounds: efficient catalysis by N-hydroxy-3,4,5,6-tetraphenylphthalimide (NHTPPI)/CuCl under mild conditions and low catalyst loading

Efficient aerobic oxidation of benzylic compounds using NHTPPI, a new NHPI analogue, as a key catalyst combined with CuCl, have been achieved under mild conditions and using as little as 1 mol% catalyst.     

Pharmacokinetic and brain distribution study of an anti-glioblastoma agent in mice by HPLC–MS/MS

Previously compound I showed great anti-glioblastoma activity without toxicity in a mouse xenograft study. In this study, a sensitive and rapid high-performance liquid chromatography–tandem mass spectrometry (HPLC–MS/MS) method was developed and validated to investigate the pharmacokinetics and brain distribution of compound I in mice. The protein precipitation method was applied to extract the compound from mouse plasma and brain homogenates, and it was then separated using a Kinetex C₁₈ column with a mobile phase consisting of acetonitrile–0.1% formic acid water (50:50, v/v). The analytes were detected with multiple reaction monitoring for the quantitative response of the compounds. The inter- and intra-day precisions were <8.29 and 3.85%, respectively, and the accuracy range was within ±7.33%. The method was successfully applied to evaluate the pharmacokinetics of compound I in mouse plasma and brain tissue. The peak concentration in plasma was achieved within 1 h. The apparent elimination half-life was 4.06 h. The peak concentration of compound I in brain tissue was 0.88 μg/g. The results indicated that compound I was rapidly distributed and could cross the blood–brain barrier. The pharmacokinetic profile summarized provides valuable information for the further investigation of compound I as a potential anti-glioblastoma agent.     

Constructing NFC-pigment composite surface treatment for enhanced paper stiffness and surface properties

The use of nano- or microfibrillar cellulose (NFC or MFC) in papermaking is generally hampered by high cost and potentially wasteful use in typical wet end applications. The solubility and fines nature of the material makes it inefficient to retain, and when retained it is generally inefficiently applied within the spatial distribution of the paper fibre matrix. To illustrate the benefits of capturing the important NFC in a layer structure to enhance surface and stiffness properties of paper and board, we present a study whereby NFC is entrapped at the surface of a fibrous web by forming an in situ composite using a porous coating layer, consisting in the exemplified case of modified calcium carbonate. It is shown that NFC can integrate itself within the porous structure providing excellent holdout and thin layer continuity essential in developing an efficient concentration of the NFC at the surface of the substrate. The effect is likened to the well-known I-beam construction. An additional feature is the potential for recycling the remaining fibrous content in the NFC or, more particularly, MFC product after the nanocrystalline cellulose (NCC) gel fraction has been absorbed, allowing for further efficient processing if needed and hence providing a potential cost reduction in the overall NFC/MFC production. The increased smoothness and uniformity obtained is illustrated by confocal laser profilometry and electron microscopy. The effect on permeability is also illustrated.     

Nonlinear rheology for threadlike micelles of tetraethylammonium perfluorooctyl sulfonate

Nonlinear rheological features were investigated for an aqueous solution of tetraethylammonium perfluorooctyl sulfonate (C₈F₁₇SO₃ ^–N⁺(C₂H₅)₄; abbreviated as FOSTEA). In the solution (c=0.045 mol/l; 28.3 g/l), spherical micelles of FOSTEA were connected with each other to form threads of pearl-necklace shape. These threads were further organized into a transient network to exhibit linear relaxation characteristic of living polymers, single-mode terminal relaxation widely separated from faster relaxation processes. Nonlinear relaxation experiments against large step-strains γ(≤8) revealed that the terminal relaxation mode had a γ-insensitive relaxation time but its relaxation intensity exhibited significant damping (much stronger than that for entangled polymers). In contrast, the relaxation time and intensity for the fast relaxation modes first increased and then decreased with increasing γ. Under shear flow, the FOSTEA threads exhibited strong thinning of the viscosity. These nonlinear features of the FOSTEA threads were compared with those of other threadlike micelles, analyzed on the basis of an empirically introduced constitutive equation, and discussed in relation to strain/low-induced scission of the living threads. Received: 20 February 1998 Accepted: 30 July 1998     

Reactivity of chemisorbed oxygen atoms and their catalytic consequences during CH4-O2 catalysis on supported Pt clusters

Kinetic and isotopic data and density functional theory treatments provide evidence for the elementary steps and the active site requirements involved in the four distinct kinetic regimes observed during CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants on Pt clusters. These four regimes exhibit distinct rate equations because of the involvement of different kinetically relevant steps, predominant adsorbed species, and rate and equilibrium constants for different elementary steps. Transitions among regimes occur as chemisorbed oxygen (O*) coverages change on Pt clusters. O* coverages are given, in turn, by a virtual O(2) pressure, which represents the pressure that would give the prevalent steady-state O* coverages if their adsorption-desorption equilibrium was maintained. The virtual O(2) pressure acts as a surrogate for oxygen chemical potentials at catalytic surfaces and reflects the kinetic coupling between C-H and O═O activation steps. O* coverages and virtual pressures depend on O(2) pressure when O(2) activation is equilibrated and on O(2)/CH(4) ratios when this step becomes irreversible as a result of fast scavenging of O* by CH(4)-derived intermediates. In three of these kinetic regimes, C-H bond activation is the sole kinetically relevant step, but occurs on different active sites, which evolve from oxygen-oxygen (O*-O*), to oxygen-oxygen vacancy (O*-*), and to vacancy-vacancy (*-*) site pairs as O* coverages decrease. On O*-saturated cluster surfaces, O*-O* site pairs activate C-H bonds in CH(4) via homolytic hydrogen abstraction steps that form CH(3) groups with significant radical character and weak interactions with the surface at the transition state. In this regime, rates depend linearly on CH(4) pressure but are independent of O(2) pressure. The observed normal CH(4)/CD(4) kinetic isotope effects are consistent with the kinetic-relevance of C-H bond activation; identical (16)O(2)-(18)O(2) isotopic exchange rates in the presence or absence of CH(4) show that O(2) activation steps are quasi-equilibrated during catalysis. Measured and DFT-derived C-H bond activation barriers are large, because of the weak stabilization of the CH(3) fragments at transition states, but are compensated by the high entropy of these radical-like species. Turnover rates in this regime decrease with increasing Pt dispersion, because low-coordination exposed Pt atoms on small clusters bind O* more strongly than those that reside at low-index facets on large clusters, thus making O* less effective in H-abstraction. As vacancies (*, also exposed Pt atoms) become available on O*-covered surfaces, O*-* site pairs activate C-H bonds via concerted oxidative addition and H-abstraction in transition states effectively stabilized by CH(3) interactions with the vacancies, which lead to much higher turnover rates than on O*-O* pairs. In this regime, O(2) activation becomes irreversible, because fast C-H bond activation steps scavenge O* as it forms. Thus, O* coverages are set by the prevalent O(2)/CH(4) ratios instead of the O(2) pressures. CH(4)/CD(4) kinetic isotope effects are much larger for turnovers mediated by O*-* than by O*-O* site pairs, because C-H (and C-D) activation steps are required to form the * sites involved in C-H bond activation. Turnover rates for CH(4)-O(2) reactions mediated by O*-* pairs decrease with increasing Pt dispersion, as in the case of O*-O* active structures, because stronger O* binding on small clusters leads not only to less reactive O* atoms, but also to lower vacancy concentrations at cluster surfaces. As O(2)/CH(4) ratios and O* coverages become smaller, O(2) activation on bare Pt clusters becomes the sole kinetically relevant step; turnover rates are proportional to O(2) pressures and independent of CH(4) pressure and no CH(4)/CD(4) kinetic isotope effects are observed. In this regime, turnover rates become nearly independent of Pt dispersion, because the O(2) activation step is essentially barrierless. In the absence of O(2), alternate weaker oxidants, such as H(2)O or CO(2), lead to a final kinetic regime in which C-H bond dissociation on *-* pairs at bare cluster surfaces limit CH(4) conversion rates. Rates become first-order in CH(4) and independent of coreactant and normal CH(4)/CD(4) kinetic isotope effects are observed. In this case, turnover rates increase with increasing dispersion, because low-coordination Pt atoms stabilize the C-H bond activation transition states more effectively via stronger binding to CH(3) and H fragments. These findings and their mechanistic interpretations are consistent with all rate and isotopic data and with theoretical estimates of activation barriers and of cluster size effects on transition states. They serve to demonstrate the essential role of the coverage and reactivity of chemisorbed oxygen in determining the type and effectiveness of surface structures in CH(4) oxidation reactions using O(2), H(2)O, or CO(2) as oxidants, as well as the diversity of rate dependencies, activation energies and entropies, and cluster size effects that prevail in these reactions. These results also show how theory and experiments can unravel complex surface chemistries on realistic catalysts under practical conditions and provide through the resulting mechanistic insights specific predictions for the effects of cluster size and surface coordination on turnover rates, the trends and magnitude of which depend sensitively on the nature of the predominant adsorbed intermediates and the kinetically relevant steps.