Molecular Lego (R): non-centrosymmetric alignment within interdigitating layers

(E)-N-Hexadecyl-4-[2-(4-octadecyloxynaphthyl) ethenyl] quinolinium bromide, which has a wide-bodied chromophore and terminal n-alkyl groups, adopts a U-shape when spread at the air-water interface but a stretched conformation when compressed to ca. 35 mN m(-1). The high-pressure phase has a narrow stability range prior to collapse but may be extended from 40 to 60 mN m(-1) by co-spreading the dye in a 1 : 1 ratio with docosanoic acid. The mixed Langmuir-Blodgett (LB) film has a monolayer thickness of 4.6 +/- 0.2 nm which decreases to 2.5 +/- 0.1 nm layer(-1) in the bulk, the reduction arising from an interdigitating layer arrangement, both top and bottom. It is the first example of LB-Lego(R) and, in addition, represents the only fully interdigitating structure with non-centrosymmetrically aligned chromophores. They are tilted 38 degrees from the substrate normal. The second-harmonic intensity increases quadratically with the number of layers, i.e. as I-(N)(2 omega) = (I(1)N2)-N-2 omega, with a second-order susceptibility of chi ((2))(zzz) = 30 pm V-1 at 1064 nm for refractive indices of n(omega) = 1.55 and n(2 omega) = 1.73, d = 2.5 nm layer(-1) and phi = 38 degrees. Angle resolved X-ray photoelectron spectra (XPS) of these films provide no evidence of the bromide counterion, which suggests that it is replaced by OH 2 or HCO3-, which occur naturally in the aqueous subphase, or C21H43COO- from the co-deposited fatty acid. This probably applies to all cationic dyes deposited by the LB technique.

A systematic approach to error isolation in computerized wastewater simulation models

Activated sludge models are used extensively in the study of wastewater treatment processes. While various commercial implementations of these models are available, there are many people who need to code models themselves using the simulation packages available to them, Quality assurance of such models is difficult. While benchmarking problems have been developed and are available, the comparison of simulation data with that of commercial models leads only to the detection, not the isolation of errors. To identify the errors in the code is time-consuming. In this paper, we address the problem by developing a systematic and largely automated approach to the isolation of coding errors. There are three steps: firstly, possible errors are classified according to their place in the model structure and a feature matrix is established for each class of errors. Secondly, an observer is designed to generate residuals, such that each class of errors imposes a subspace, spanned by its feature matrix, on the residuals. Finally. localising the residuals in a subspace isolates coding errors. The algorithm proved capable of rapidly and reliably isolating a variety of single and simultaneous errors in a case study using the ASM 1 activated sludge model. In this paper a newly coded model was verified against a known implementation. The method is also applicable to simultaneous verification of any two independent implementations, hence is useful in commercial model development.

Molecular basis by which garlic suppresses atherosclerosis

The aim of this study was to determine the mechanism by which the aged garlic extract Kyolic has a protective effect against atherosclerosis. Plasma cholesterol of rabbits fed a 1% cholesterol-enriched diet for 6 wk was not reduced by supplementation with 800 muL Kyolic/(kg body . d). In spite of this, Kyolic reduced by 64% (P < 0.05) the surface area of the thoracic aorta covered by fatty streaks and significantly reduced aortic arch cholesterol. Kyolic also significantly inhibited by 50% the development of thickened, lipid-filled lesions in preformed neointimas produced by Fogarty 2F balloon catheter injury of the right carotid artery in cholesterol-fed rabbits. In vitro studies found that Kyolic completely prevented vascular smooth muscle phenotypic change from the contractile. high volume fraction of filament (V(v)myo) state, and inhibited proliferation of smooth muscle cells in the synthetic state with a 50% effective dose (ED50) of 0.2%. Kyolic also slightly inhibited the accumulation of lipid in cultured macrophages but not smooth muscle, and had no effect an the expression of adhesion molecules on the surface of the endothelium or the adherence of leukocytes. It is concluded that Kyolic exerts antiatherogenic effects through inhibition of smooth muscle phenotypic change and proliferation, and by another (unclarified) effect on lipid accumulation in the artery wall.

Time-dependent master equation simulation of complex elementary reactions in combustion: Application to the reaction of (CH2)-C-1 with C2H2 from 300-2000 K

Computational simulations of the title reaction are presented, covering a temperature range from 300 to 2000 K. At lower temperatures we find that initial formation of the cyclopropene complex by addition of methylene to acetylene is irreversible, as is the stabilisation process via collisional energy transfer. Product branching between propargyl and the stable isomers is predicted at 300 K as a function of pressure for the first time. At intermediate temperatures (1200 K), complex temporal evolution involving multiple steady states begins to emerge. At high temperatures (2000 K) the timescale for subsequent unimolecular decay of thermalized intermediates begins to impinge on the timescale for reaction of methylene, such that the rate of formation of propargyl product does not admit a simple analysis in terms of a single time-independent rate constant until the methylene supply becomes depleted. Likewise, at the elevated temperatures the thermalized intermediates cannot be regarded as irreversible product channels. Our solution algorithm involves spectral propagation of a symmetrised version of the discretized master equation matrix, and is implemented in a high precision environment which makes hitherto unachievable low-temperature modelling a reality.

Using clusters of computers for large QU-GENE simulation experiments

The QU-GENE Computing Cluster (QCC) is a hardware and software solution to the automation and speedup of large QU-GENE (QUantitative GENEtics) simulation experiments that are designed to examine the properties of genetic models, particularly those that involve factorial combinations of treatment levels. QCC automates the management of the distribution of components of the simulation experiments among the networked single-processor computers to achieve the speedup.

Recent advances in processing and characterization of periodic mesoporous MCM-41 silicate molecular sieves

The discovery of periodic mesoporous MCM-41 and related molecular sieves has attracted significant attention from a fundamental as well as applied perspective. They possess well-defined cylindrical/hexagonal mesopores with a simple geometry, tailored pore size, and reproducible surface properties. Hence, there is an ever-growing scientific interest in the challenges posed by their processing and characterization and by the refinement of various sorption models. Further, MCM-41-based materials are currently under intense investigation with respect to their utility as adsorbents, catalysts, supports, ion-exchangers, and molecular hosts. In this article, we provide a critical review of the developments in these areas with particular emphasis on adsorption characteristics, progress in controlling the pore sizes, and a comparison of pore size distributions using traditional and newer models. The model proposed by the authors for adsorption isotherms and criticalities in capillary condensation and hysteresis is found to explain unusual adsorption behavior in these materials while providing a convenient characterization tool.

The use of liquid phase adsorption isotherms for characterization of activated carbons

The characterization of three commercial activated carbons was carried out using the adsorption of various compounds in the aqueous phase. For this purpose the generalized adsorption isotherm was employed, and a modification of the Dubinin-Radushkevich pore filling model, incorporating repulsive contributions to the pore potential as well as bulk liquid phase nonideality, was used as the local isotherm. Eight different flavor compounds were used as adsorbates, and the isotherms were jointly fitted to yield a common pore size distribution for each carbon. The bulk liquid phase nonideality was incorporated through the UNIFAC activity coefficient model, and the repulsive contribution to the pore potential was incorporated through the Steele 10-4-3 potential model. The mean micropore network coordination number for each carbon was also determined from the fitted saturation capacity based on percolation theory. Good agreement between the model and the experimental data was observed. In addition, excellent agreement between the bimodal gamma pore size distribution and density functional theory-cum-regularization-based pore size distribution obtained by argon adsorption was also observed, supporting the validity of the model. The results show that liquid phase adsorption, using adsorptive molecules of different sizes, can be an effective means of characterizing the pore size distribution as well as connectivity. Alternately, if the carbon pore size distribution is independently known, the method can be used to measure critical molecular sizes. (C) 2001 Elsevier Science.

A simulation model for analysing patient activity in dermatology

We developed a general model to assess patient activity within the primary and secondary health-care sectors following a dermatology outpatient consultation. Based on observed variables from the UK teledermatology trial, the model showed that up to 11 doctor-patient interactions occurred before a patient was ultimately discharged from care. In a cohort of 1000 patients, the average number of health-care visits was 2.4 (range 1-11). Simulation analysis suggested that the most important parameter affecting the total number of doctor-patient Interactions is patient discharge from care following the initial consultation. This implies that resources should be concentrated in this area. The introduction of teledermatology (either realtime or store and forward) changes the values of the model parameters. The model provides a quantitative tool for planning the future provision of dermatology health-care.

Aluminophosphate-based mesoporous molecular sieves: Synthesis and characterization of TAPOs

Mesoporous Ti-substituted aluminophosphates (AlPOs) with a hexagonal, cubic and lamellar pore structure, characteristic of MCM-41, MCM-48, and MCM-50, respectively, were synthesized. The stability of these mesophases upon template removal was studied. The pore structures, surface properties, and local atom environments of Al, P, and Ti of the hexagonal and cubic Ti-containing mesoporous products were extensively characterized using X-ray diffraction, magic angle spinning nuclear magnetic resonance, AAS, XPS, ultraviolet–visible, and adsorption of nitrogen and water vapor techniques while the lamellar mesophase was not further characterized due to its very poor thermal stability. Ti-containing mesoporous AlPO materials show a reasonable thermal stability upon template removal, a hydrophilic surface property, and high porosity showing application potentials in catalytic oxidation of hydrocarbons.

Vitamin B12 and hepatitis C: Molecular biology and human pathology

Cobalamins are stored in high concentrations in the human liver and thus are available to participate in the regulation of hepatotropic virus functions. We show that cyanocobalamin (vitamin B12) inhibited the H(IV internal ribosome entry site (IRES)-dependent translation of a reporter gene in vitro in a dose-dependent manner without significantly affecting the cap-dependent mechanism. Vitamin B12 failed to inhibit translation by IRES elements from encephalomyocarditis virus (EMCV) or classical swine fever virus (CSFV), We also demonstrate a relationship between the total cobalamin concentration in human sera and HCV viral load (a measure of viral replication in the host), The mean viral load was two orders of magnitude greater when the serum cobalamin concentration was above 200 pM (P < 0.003), suggesting that the total cobalamin concentration in an HCV-infected liver is biologically significant in HCV replication.

Hydrophobicity of Templated Silica Xerogels for Molecular Sieving Applications

Silica xerogels were prepared by a sol-gel process catalyzed by acid with tetraethylorthosilicate, and using an organic covalent ligand template (methyltriethoxysilane) or a noncovalent template C6 surfactant (triethylhexylammonium bromide). The influence of hydrotreatment on the structure of templated xerogels is examined in terms of surface area, micropore volume, average pore size, and pore size distribution, and compared against a blank xerogel (nontemplated). The role of surface functional groups was evaluated using Si-29 nuclear magnetic resonance. The structural integrity of the xerogel was maintained to a large extent in samples that had a high contribution of Q(4) species (siloxane groups). Xerogel matrix densification occurred when there was a large concentration of Q(3) and Q(2) species (silanol groups), which also were responsible for increased hydrophilicity. The templated xerogels resulted in up to a 25% concentration of methyl functional groups (T-3 and T-2 species), leading to hydrophobic xerogels. The best results in terms of structural integrity and hydrophobicity were obtained with templated xerogels prepared with the C6 surfactant. The results in this study suggest that surfactant-enhanced condensation reactions lead to structures with a high contribution of Q(4) groups, which are not susceptible to water attack, but are strong enough to oppose matrix densification during rehydration.

Non-Markovian homodyne-mediated feedback on a two-level atom: a quantum trajectory treatment

Quantum feedback can stabilize a two-level atom against decoherence (spontaneous emission), putting it into an arbitrary (specified) pure state. This requires perfect homodyne detection of the atomic emission, and instantaneous feedback. Inefficient detection was considered previously by two of us. Here we allow for a non-zero delay time tau in the feedback circuit. Because a two-level atom is a non-linear optical system, an analytical solution is not possible. However, quantum trajectories allow a simple numerical simulation of the resulting non-Markovian process. We find the effect of the time delay to be qualitatively similar to chat of inefficient detection. The solution of the non-Markovian quantum trajectory will not remain fixed, so that the time-averaged state will be mixed, not pure. In the case where one tries to stabilize the atom in the excited state, an approximate analytical solution to the quantum trajectory is possible. The result, that the purity (P = 2Tr[rho (2)] - 1) of the average state is given by P = 1 - 4y tau (where gamma is the spontaneous emission rate) is found to agree very well with the numerical results. (C) 2001 Elsevier Science B.V. All rights reserved.

Characterisation of templated xerogels for molecular sieve application

This paper presents the results of the characterisation of templated silica xerogels as precursor material for molecular sieve silica membranes for gas separation. The template agent integrated in the xerogel matrix is a methyl ligand covalently bended to the siloxane network in the form of methyltriethoxysilane (MTES). Several surface and microstructural characterisation techniques such as TGA, FTIR, NMR, and nitrogen adsorption have been employed to obtain information on the reaction mechanisms involved in the sol-gel processing of such molecular sieves. The characterisation results show the effects of processing parameters such as heat treatment temperature, and the concentration of the covalently bonded template on the development of the pore structure. It was found that calcination temperature significantly enhanced the condensation reactions thus resulted in more Si-O-Si groups being formed. This was also confirmed with the data of FTIR characterisation showing enhanced silicon bands at higher heat treatment temperatures. As a result of the promoted densification and shrinkable pore network the micropore volume also reduced with increasing methyl ligand molar ratio. However, the mean pore diameter does not change significantly with calcination temperature. While the contribution of the templates towards controlling pore size is less precise, increasing the methyl ligand molar ratio results in the broadening of the pore size distribution and lower pore volume. Higher template concentration induces the collapse of the xerogel matrix due to capillary stress promoting dense xerogels with low pore volume (C) 2001 Elsevier Science B.V. All rights reserved.

Genetic variability in Australian isolates of Puccinia coronata f. sp avenae assessed with molecular and pathogenicity markers

In a preliminary survey of genetic variability among 12 Australian isolates of Puccinia coronata f. sp. avenae Fraser and Led (Pca) collected from 1966 to 1993, two relatively diverse (