Limits to gelation in colloidal aggregation

We show that the dynamics of large fractal colloid aggregates are well described by a combination of translational and rotational diffusion and internal elastic fluctuations, allowing both the aggregate size and internal elasticity to be determined by dynamic light scattering. The comparison of results obtained in microgravity and on Earth demonstrates that cluster growth is limited by gravity-induced restructuring. In the absence of gravity, thermal fluctuations ultimately inhibit fractal growth and set the fundamental limitation to the lowest volume fraction which will gel.     

Analysis of the flow in inhomogeneous particle beds using the spatially averaged two-fluid equations

The drag force term appearing in two-fluid models for fluid–particle flows is commonly closed by expressing it as a function of the local quantities, such as the local particle volume fraction, the local slip velocity between the particle and fluid phases, and the local mean-squared fluctuating velocity of the particles. The adequacy of such closures for inhomogeneous suspensions has been debated in the literature and some researchers have suggested the need for additional terms involving spatial gradients in these quantities. To test this proposition, simulations of flow in inhomogeneous steady beds of particles have been performed using the lattice-Boltzmann method. The particle beds consisted of disordered assemblies with a density profile on a scale much larger than the particle radius. Inhomogeneous beds with a controlled density profile were generated in three different ways, (i) by inhomogeneous stretching of the particle bed in one direction, (ii) by applying an inhomogeneous force to the particle phase during random motion of the particles, and (iii) by taking snapshots of a direct simulation of a traveling wave in a fluidization simulation. The global structure of the three beds was comparable, while assessment of the radial distribution functions showed that the three beds exhibited clearly different microscopic structures.     

A new strategy for fast radiofrequency CW EPR imaging: direct detection with rapid scan and rotating gradients

Rapid field scan on the order of T/s using high frequency sinusoidal or triangular sweep fields superimposed on the main Zeeman field, was used for direct detection of signals without low-frequency field modulation. Simultaneous application of space-encoding rotating field gradients have been employed to perform fast CW EPR imaging using direct detection that could, in principle, approach the speed of pulsed FT EPR imaging. The method takes advantage of the well-known rapid-scan strategy in CW NMR and EPR that allows arbitrarily fast field sweep and the simultaneous application of spinning gradients that allows fast spatial encoding. This leads to fast functional EPR imaging and, depending on the spin concentration, spectrometer sensitivity and detection band width, can provide improved temporal resolution that is important to interrogate dynamics of spin perfusion, pharmacokinetics, spectral spatial imaging, dynamic oxymetry, etc.     

An ab initio and matrix isolation infrared study of the 1:1 C2H2–CHCl3 adduct

The details of weak C–Hπ interactions that control several inter and intramolecular structures have been studied experimentally and theoretically for the 1:1 C₂H₂–CHCl₃ adduct. The adduct was generated by depositing acetylene and chloroform in an argon matrix and a 1:1 complex of these species was identified using infrared spectroscopy. Formation of the adduct was evidenced by shifts in the vibrational frequencies compared to C₂H₂ and CHCl₃ species. The molecular structure, vibrational frequencies and stabilization energies of the complex were predicted at the MP2/6-311+G(d,p) and B3LYP/6-311+G(d,p) levels. Both the computational and experimental data indicate that the C₂H₂–CHCl₃ complex has a weak hydrogen bond involving a C–Hπ interaction, where the C₂H₂ acts as a proton acceptor and the CHCl₃ as the proton donor. In addition, there also appears to be a secondary interaction between one of the chlorine atoms of CHCl₃ and a hydrogen in C₂H₂. The combination of the C–Hπ interaction and the secondary ClH interaction determines the structure and the energetics of the C₂H₂–CHCl₃ complex. In addition to the vibrational assignments for the C₂H₂–CHCl₃ complex we have also observed and assigned features owing to the proton accepting C₂H₂ submolecule in the acetylene dimer.     

Parameter estimation based on interval-valued belief structures

Parameter estimation based on uncertain data represented as belief structures is one of the latest problems in the Dempster–Shafer theory. In this paper, a novel method is proposed for the parameter estimation in the case where belief structures are uncertain and represented as interval-valued belief structures. Within our proposed method, the maximization of likelihood criterion and minimization of estimated parameter’s uncertainty are taken into consideration simultaneously. As an illustration, the proposed method is employed to estimate parameters for deterministic and uncertain belief structures, which demonstrates its effectiveness and versatility.     

A quantile based test for comparing cumulative incidence functions of competing risks models

In the present note, we develop a nonparametric testing procedure for testing equality of cumulative incidence functions of competing risks models using quantile functions. Asymptotic properties of the test statistic are discussed. Simulation studies and real data examples illustrate the practical utility of the procedure.     

On waiting time distributions for patterns in a sequence of multistate trials

In this paper, we consider the waiting time distributions for patterns in a sequence of multistate trials. A simple and general framework, using the Markov chain imbedding method, is developed to study the waiting time distributions of both simple and compound patterns. Algorithms for the computation of these are given. The general theory is employed for the investigation of some examples in order to illustrate the theoretical results.     

Photophysics of untethered ZnTPP-fullerene complexes in solution

The spectroscopy and dynamic behavior of the self-assembled, Soret-excited zinc tetraphenylporphyrin (ZnTPP) plus fullerene (C(60)) model system in solution has been examined using steady state fluorescence quenching, nanosecond time-correlated single photon counting, picosecond fluorescence upconversion, and picosecond transient absorption methods. Evidence of ground state complexation is presented. Steady-state quenching of the S(2) and S(1) fluorescence of ZnTPP by C(60) reveals that the quenching processes only occur in the excited complexes, are ultrafast, and proceed at different rates in the two states. Only uncomplexed ZnTPP is observed by fluorescence lifetime methods; the locally excited complexes are either dark or, more likely, rapidly relax to products that do not radiate strongly. Both short-range (Dexter) energy transfer and electron transfer relaxation mechanisms are evaluated. Picosecond transient absorption data obtained from the subtle differences between the spectra of Soret-excited ZnTPP with and without a large excess of added C(60) reveal the formation, on a subpicosecond time scale, of relatively long-lived charge-separated species. Soret excitation of ZnTPP···C(60) does not produce a quantitative yield of species in the lower S(1) excited state.