Molecular dynamics and alignment studies of silica-filled 4-pentyl-4′-cyanobiphenyl (5CB) liquid crystal

A comprehensive study of the dielectric properties of 4-pentyl-4′-cyanobiphenyl (5CB) liquid crystal filled with silica particles (particle size 30–80 nm, concentration 2, 3, 5, 10 and 15 wt%). Dielectric spectroscopy in the frequency range 100 to 10 7 Hz was applied to investigate the influence of the filler on the dynamic behaviour of the liquid crystal molecules in both the nematic and isotropic phases. In this frequency range one relaxation process is observed (at f>10⁶ Hz). The dynamical behaviour of the 5CB liquid crystal is described by the Cole-Cole relaxation function. The temperature dependence of the relaxation time obeys the empirical Arrhenius equation. The activation energies are approximately 75 kJ mol¹ for the pure 5CB sample in the nematic phase and 50 kJ mol¹ for the 5 wt% silica-filled 5CB sample. These values are compared with the corresponding literature values. The reversible electro-mechanical response of these samples under the influence of an applied a.c. electric field is investigated.     

Dye-coated europium monosulfide

Nanoparticles of EuS were synthesized using europium dithiocarbamate complexes. The resulting nanoparticles were coated with the dye, 1-pyrene carboxylic acid and the resulting material was characterized using X-ray powder diffraction, TEM, and UV-visible spectroscopy. Fluorescence spectroscopy was used to determine the relative energy of the conduction band edge to the excited state energy of the dye.     

Molecular alignment of the 4-octyl-4'-cyanobiphenyl liquid crystal filled with SiO2

The molecular dynamics and molecular alignment of the dispersed 4-octyl-4'-cyanobiphenyl (8CB) liquid crystal with 5 wt % of SiO₂ nanosphere particles have been studied using dielectric spectroscopy. The measurements were performed in the frequency range between 10²-10⁷ Hz in the SmA, N and I phases. The results show only one Debye relaxation process at high frequency (10⁵-10⁷ Hz). In the bulk material, activation energies of 40, 58 and 63 kJ mol^-1 were determined for the SmA, N and the I phases, respectively. In the dispersed sample, the activation energies were found to be 52, 76 and 81 kJ mol^-1, respectively. These results are compared with the available data in the literature. The reversible electromechanical response of the dispersed sample under the influence of an applied a.c. electric field was investigated in the SmA, N, and I phases.     

A general model for batch building processes under the timeout and capacity rules

In manufacturing systems, batch building processes are very common, as goods are often transported or processed in batches and must therefore be collected before these transport or processing steps can occur. In this paper, we present a method for the performance analysis of general batch building processes in material flow systems under the timeout and capacity rules. The proposed model allows for stochastic collecting times and incorporates no restrictions with respect to the number of arriving units and their interarrival times. The accuracy of the discrete-time approach is demonstrated by comparing this approach with a discrete-event simulation model in continuous-time. Subsequently, the model is applied to two cases: a transportation case from the health care industry and the process of building a batch for a batch processor.     

The impact of sampling time on peak capacity and analysis speed in on-line comprehensive two-dimensional liquid chromatography

Comprehensive two-dimensional liquid chromatography (2DLC) offers a number of practical advantages over optimized one-dimensional LC in peak capacity and thus in resolving power. The traditional “product rule” for overall peak capacity for a 2DLC system significantly overestimates peak capacity because it neglects under-sampling of the first dimension separation. Here we expand on previous work by more closely examining the effects of the first dimension peak capacity and gradient time, and the second dimension cycle times on the overall peak capacity of the 2DLC system. We also examine the effects of re-equilibration time on under-sampling as measured by the under-sampling factor and the influence of molecular type (peptide vs. small molecule) on peak capacity. We show that in fast 2D separations (less than 1 h), the second dimension is more important than the first dimension in determining overall peak capacity and conclude that extreme measures to enhance the first dimension peak capacity are usually unwarranted. We also examine the influence of sample types (small molecules vs. peptides) on second dimension peak capacity and peak capacity production rates, and how the sample type influences optimum second dimension gradient and re-equilibration times.     

Block‐triangular preconditioners for PDE‐constrained optimization

In this paper we investigate the possibility of using a block‐triangular preconditioner for saddle point problems arising in PDE‐constrained optimization. In particular, we focus on a conjugate gradient‐type method introduced by Bramble and Pasciak that uses self‐adjointness of the preconditioned system in a non‐standard inner product. We show when the Chebyshev semi‐iteration is used as a preconditioner for the relevant matrix blocks involving the finite element mass matrix that the main drawback of the Bramble–Pasciak method—the appropriate scaling of the preconditioners—is easily overcome. We present an eigenvalue analysis for the block‐triangular preconditioners that gives convergence bounds in the non‐standard inner product and illustrates their competitiveness on a number of computed examples. Copyright © 2010 John Wiley & Sons, Ltd.     

Effects of surface site distribution and dielectric discontinuity on the charging behavior of nanoparticles: a grand canonical Monte Carlo study

The surface site distribution and the dielectric discontinuity effects on the charging process of a spherical nanoparticle (NP) have been investigated. It is well known that electrostatic repulsion between charges on neighbouring sites tends to decrease the effective charge of a NP. The situation is more complicated close to a dielectric breakdown, since here a charged site is not only interacting with its neighbours but also with its own image charge and the image charges of all its neighbours. Coexistence of opposite charges, titration sites positions, and pH dependence are systematically studied using a grand canonical Monte Carlo method. A Tanford and Kirkwood approach has been applied to describe the interaction potentials between explicit discrete ampholytic charging sites. Homogeneous, heterogeneous and patch site distributions were considered to reproduce the titration site distribution at the solid/solution interface of natural NPs. Results show that the charging process is controlled by the balance between Coulomb interactions and the reaction field through the solid-liquid interface. They also show that the site distribution plays a crucial role in the charging process. In patch distributions, charges accumulate at the perimeter of each patch due to finite size effects. When homogeneous and heterogeneous distributions are compared, three different charging regimes are obtained. In homogeneous and heterogeneous (with quite low polydispersity indexes) distributions, the effects of the NP dielectric constant on Coulomb interactions are counterbalanced by the reaction field and in this case, the dielectric breakdown has no significant effect on the charging process. This is not the case in patch distributions, where the dielectric breakdown plays a crucial role in the charging process.     

Shape resonances in slow electron scattering by aromatic molecules. I. Anthraquinone derivatives

A series of anthraquinone (C(14)O(2)H(8)) derivatives has been studied by means of electron capture negative ion mass spectrometry (ECNI-MS), photoelectron spectroscopy (PES), and AM1 quantum chemical calculations. Mean lifetimes of molecular negative ions M(-.) (MNI) have been measured. The mechanism of long-lived MNI formation in the epithermal energy region of incident electrons has been investigated. A simple model of a molecule (a spherical potential well with the repulsive centrifugal term) has been applied for the analysis of the energy dependence of cross sections at the first stage of the electron capture process. It has been shown that a temporary resonance of MNI at the energy approximately 0.5 eV corresponds to a shape resonance with lifetime 1-2.10(-13) s in the f-partial wave (l = 3) of the incident electron. The next resonant state of MNI at the energy approximately 1.7 eV has been associated with the electron excited Feshbach resonance (whose parent state is a triplet npi* transition). In all cases the initial electron state of the MNI relaxes into the ground state by means of a radiationless transition, and the final state of the MNI is a nuclear excited resonance with a lifetime measurable on the mass spectrometry timescale. Copyright 1999 John Wiley & Sons, Ltd.     

Study of 290 cases of polyhydramnios and congenital malformations in a series of 225,669 consecutive births

OBJECTIVES: To provide data on polyhydramnios associated with congenital anomalies in 225,669 consecutive pregnancies. MATERIAL AND METHODS: The information in this study came from births of known outcome recorded in our registry of congenital malformations. Routine ultrasonographic examination was performed. Polyhydramnios was diagnosed ultrasonographically. A case-control study allowed the examination of genetic and environmental causal factors of polyhydramnios associated with congenital malformations. RESULTS: The prevalence of this association was 1.28/1,000 (290 cases). Polyhydramnios associated with congenital malformations was diagnosed prenatally in 44.5% of the cases, 10.3% of the infants were stillborn. Forty-one percent of the cases had more than one malformation, 14.5% had a chromosomal aberration, and 20.0% had multiple malformations that do not constitute a syndrome. The more frequent malformations associated with polyhydramnios were cardiac, digestive, central nervous system, musculoskeletal, and urinary. There was increased parental consanguinity. The incidence of polyhydramnios and congenital anomalies among first-degree relatives was 4.1% and first-degree relatives had more malformations than controls (6.2 vs. 3.2%, p < 0.05). Threatened abortions and diabetes mellitus were significantly more frequent among mothers of children with congenital malformations associated with polyhydramnios than among controls. CONCLUSIONS: Our study demonstrated that careful fetal examination has to be performed when polyhydramnios is diagnosed as congenital malformations are often associated with polyhydramnios. We recommend the use of fetal chromosome analysis and careful ultrasonographic examination in every pregnancy complicated by polyhydramnios.