Condensation of all-cis-tetraphenylcyclotetrasiloxanetetraol in ammonia: new method for preparation of ladder-like polyphenylsilsesquioxanes

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Purcell Effect and Nonlinear Behavior of the Emission in a Periodic Structure Composed of InAs Monolayers Embedded in a GaAs Matrix

Enhancement of spontaneous emission in a resonant Bragg quantum well (QW) structure with 60 periods of triple InAs monolayers embedded in a GaAs matrix is studied experimentally and theoretically. From measurements of the time‐resolved photoluminescence, besides the QW exciton at 1.47 eV, a specific super‐radiant (SR) emission demonstrating nonlinear properties is found. The SR mode shows a near‐quadratic dependence of intensity on excitation power, while its energy position follows the Bragg condition. It is revealed that the SR mode shows a peculiar non‐monotonic dependence of intensity on direction, with a maximum observed at approximately 40°. The enhancement in the SR emission at a specific direction is correlated well with suggested theoretical consideration of the modal Purcell factor for periodic quantum well structures.     

The Sample Average Approximation Method Applied to Stochastic Routing Problems: A Computational Study

The sample average approximation (SAA) method is an approach for solving stochastic optimization problems by using Monte Carlo simulation. In this technique the expected objective function of the stochastic problem is approximated by a sample average estimate derived from a random sample. The resulting sample average approximating problem is then solved by deterministic optimization techniques. The process is repeated with different samples to obtain candidate solutions along with statistical estimates of their optimality gaps.We present a detailed computational study of the application of the SAA method to solve three classes of stochastic routing problems. These stochastic problems involve an extremely large number of scenarios and first-stage integer variables. For each of the three problem classes, we use decomposition and branch-and-cut to solve the approximating problem within the SAA scheme. Our computational results indicate that the proposed method is successful in solving problems with up to 2¹⁶⁹⁴ scenarios to within an estimated 1.0% of optimality. Furthermore, a surprising observation is that the number of optimality cuts required to solve the approximating problem to optimality does not significantly increase with the size of the sample. Therefore, the observed computation times needed to find optimal solutions to the approximating problems grow only linearly with the sample size. As a result, we are able to find provably near-optimal solutions to these difficult stochastic programs using only a moderate amount of computation time.     

Molecular dynamics and information on possible sites of interaction of intramyocellular metabolites in vivo from resolved dipolar couplings in localized H NMR spectra

Proton NMR resonances of the endogenous metabolites creatine and phosphocreatine ((P)Cr), taurine (Tau), and carnosine (Cs, β-alanyl-l-histidine) were studied with regard to residual dipolar couplings and molecular mobility. We present an analysis of the direct ¹H–¹H interaction that provides information on motional reorientation of subgroups in these molecules in vivo. For this purpose, localized ¹H NMR experiments were performed on m. gastrocnemius of healthy volunteers using a 1.5-T clinical whole-body MR scanner. We evaluated the observable dipolar coupling strength SD₀ (S = order parameter) of the (P)Cr-methyl triplet and the Tau-methylene doublet by means of the apparent line splitting. These were compared to the dipolar coupling strength of the (P)Cr-methylene doublet. In contrast to the aliphatic protons of (P)Cr and Tau, the aromatic H2 (δ = 8 ppm) and H4 (δ = 7 ppm) protons of the imidazole ring of Cs exhibit second-order spectra at 1.5 T. This effect is the consequence of incomplete transition from Zeeman to Paschen-Back regime and allows a determination of SD₀ from H2 and H4 of Cs as an alternative to evaluating the multiplet splitting which can be measured directly in high-resolution ¹H NMR spectra. Experimental data showed striking differences in the mobility of the metabolites when the dipolar coupling constant D₀ (calculated with the internuclear distance known from molecular geometry in the case of complete absence of molecular dynamics and motion) is used for comparison. The aliphatic signals involve very small order parameters S ≈ (1.4 − 3) × 10⁻⁴ indicating rapid reorientation of the corresponding subgroups in these metabolites. In contrast, analysis of the Cs resonances yielded S ≈ (113 − 137) × 10⁻⁴. Thus, the immobilization of the Cs imidazole ring owing to an anisotropic cellular substructure in human m. gastrocnemius is much more effective than for (P)Cr and Tau subgroups. Furthermore, ¹H NMR experiments on aqueous model solutions of histidine and N-acetyl-l-aspartate (NAA) enabled the assignment of an additional signal component at δ = 8 ppm of Cs in vivo to the amide group at the peptide bond. The visibility of this proton could result from hydrogen bonding which would agree with the anticipated stronger motional restriction of Cs. Referring to the observation that all dipolar-coupled multiplets resolved in localized in vivo ¹H NMR spectra of human m. gastrocnemius collapse simultaneously when the fibre structure is tilted towards the magic angle (θ ≈ 55°), a common model for molecular confinement in muscle tissue is proposed on the basis of an interaction of the studied metabolites with myocellular membrane phospholipids.     

Piecewise Deterministic Markov Control Processes with Feedback Controls and Unbounded Costs

The control of piecewise-deterministic processes is studied where only local boundedness of the data is assumed. Moreover the discount rate may be zero. The value function is shown to be solution to the Bellman equation in a weak sense; however the solution concept is strong enough to generate optimal policies. Continuity and compactness conditions are given for the existence of nonrelaxed optimal feedback controls.     

Kinetics of the bromate–bromide reaction at high bromide concentrations

At bromide concentrations higher than 0.1 M, a second term must be added to the classical rate law of the bromate–bromide reaction that becomes ?d[BrO₃^?]/dt = [BrO₃^?][H⁺]²(k₁[Br^?] + k₂[Br^?]²). In perchloric solutions at 25°C, k₁ = 2.18 dm³ mol^?3 s^?1 and k₂ = 0.65 dm⁴ mol^?4 s^?1 at 1 M ionic strength and k₁ = 2.60 dm³ mol³ s^?1and k₂ = 1.05 dm⁴ mol^?4 s^?1 at 2 M ionic strength. A mechanism explaining this rate law, with Br₂O₂ as key intermediate species, is proposed. Errors that may occur when using the Guggenheim method are discussed. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 39: 17–21, 2007     

Formation of functional groups on graphite during oxygen plasma treatment

Improved sample wettability was obtained by oxygen plasma functionalization of pyrolytic graphite. The samples were exposed to highly dissociated oxygen plasma with the density of 1 × 10¹⁶ m⁻³, the electron temperature of about 5.5 eV and the density of neutral oxygen atoms of 8 × 10²¹ m⁻³ for 20 s. The surface wettability was measured by a contact angle of water drop. The contact angle dropped from original 112° down to about 1°. The functional groups were detected by XPS analyses. The survey spectrum showed a substantial increase of oxygen concentration on the surface, while high-resolution analyses showed additional oxygen was bonded onto the graphite surface in the form of C-O polar functional group responsible for the increase of the surface energy.