Isomerization dynamics in viscous liquids: Microscopic investigation of the coupling and decoupling of the rate to and from solvent viscosity and dependence on the intermolecular potential

A detailed investigation of viscosity dependence of the isomerization rate is carried out for continuous potentials by using a fully microscopic, self-consistent mode-coupling theory calculation of both the friction on the reactant and the viscosity of the medium. In this calculation we avoid approximating the short time response by the Enskog limit, which overestimates the friction at high frequencies. The isomerization rate is obtained by using the Grote-Hynes formula. The viscosity dependence of the rate has been investigated for a large number of thermodynamic state points. Since the activated barrier crossing dynamics probes the high-frequency frictional response of the liquid, the barrier crossing rate is found to be sensitive to the nature of the reactant-solvent interaction potential. When the solute-solvent interaction is modeled by a 6-12 Lennard-Jones potential, we find that over a large variation of viscosity (eta), the rate (k) can indeed be fitted very well to a fractional viscosity dependence: (k similar to eta(-alpha)), with the exponent alpha in the range 1 greater than or equal to alpha >0. The calculated values of the exponent appear to be in very good agreement with many experimental results. In particular, the theory, for the first time, explains the experimentally observed high value of alpha even at the barrier frequency, omega(b). similar or equal to 9 X 10(12) s(-1) for the isomerization reaction of 2-(2'-propenyl)anthracene in liquid eta-alkanes. The present study can also explain the reason for the very low value of vb observed in another study for the isomerization reaction of trans-stilbene in liquid n-alkanes. For omega(b) greater than or equal to 2.0 X 10(13) s(-1), we obtain alpha similar or equal to 0, which implies that the barrier crossing rate becomes identical to the transition-state theory predictions. A careful analysis of isomerization reaction dynamics involving large amplitude motion suggests that the barrier crossing dynamics itself may become irrelevant in highly viscous liquids and the rate might again be coupled directly to the viscosity. This crossover is predicted to be strongly temperature dependent and could be studied by changing the solvent viscosity by the application of pressure. (C) 1999 American Institute of Physics. [S0021-9606(9950514-X].

Continuous distribution kinetics for the thermal degradation of LDPE in solution

Polymer degradation in solution has several advantages over melt pyrolysis, The degradation of low-density polyethylene (LDPE) occurs at much lower temperatures in solution (280-360degreesC) than in conventional melt pyrolysis (400-450degreesC). The thermal degradation kinetics of LDPE in solution was investigated in this work. LDPE was dissolved in liquid paraffin and degraded for 3 h at various temperatures (280-360degreesC). Samples were taken at specific times and analyzed with high-pressure liquid chromatography/gel permeation chromatography for the molecular weight distribution (MWD), The time evolution of the MWD was modeled with continuous distribution kinetics. Data indicated that LDPE followed random-chain-scission degradation. The rapid initial drop in molecular weight, observed up to 45 min, was attributed to the presence of weak links in the polymer. The rate coefficients for the breakage of weak and strong links were determined, and the corresponding average activation energies were calculated to be 88 and 24 kJ/mol, respectively. (C) 2002 John Wiley Sons, Inc.

Continuous distribution kinetics for ultrasonic degradation of poly(methyl methacrylate)

Ultrasonic degradation of poly(methyl methacrylate) (PMMA) was carried out in several solvents and some mixtures of solvents. The time evolution of molecular weight distribution (MWD), determined by gel permeation chromatography, is analysed by continuous distribution kinetics. The rate coefficients for polymer degradation are determined for each solvent. The variation of rate coefficients is correlated with the vapour pressure of the solvent, kinematic viscosity of the solution and solvent-polymer interaction parameters. The vapour pressure and the kinematic viscosity of the solution are found to be more critical than other parameters (such as the Huggins and Flory-Huggins constants) in determining the degradation rates. (C) 2001 Society of Chemical Industry.

High-rate analysis of channel-optimized vector quantization

High-rate analysis of channel-optimized vector quantizationThis paper considers the high-rate performance of channel optimized source coding for noisy discrete symmetric channels with random index assignment. Specifically, with mean squared error (MSE) as the performance metric, an upper bound on the asymptotic (i.e., high-rate) distortion is derived by assuming a general structure on the codebook. This structure enables extension of the analysis of the channel optimized source quantizer to one with a singular point density: for channels with small errors, the point density that minimizes the upper bound is continuous, while as the error rate increases, the point density becomes singular. The extent of the singularity is also characterized. The accuracy of the expressions obtained are verified through Monte Carlo simulations.

High-Rate Vector Quantization for Noisy Channels With Applications to Wideband Speech Spectrum Compression

This paper considers the high-rate performance of source coding for noisy discrete symmetric channels with random index assignment (IA). Accurate analytical models are developed to characterize the expected distortion performance of vector quantization (VQ) for a large class of distortion measures. It is shown that when the point density is continuous, the distortion can be approximated as the sum of the source quantization distortion and the channel-error induced distortion. Expressions are also derived for the continuous point density that minimizes the expected distortion. Next, for the case of mean squared error distortion, a more accurate analytical model for the distortion is derived by allowing the point density to have a singular component. The extent of the singularity is also characterized. These results provide analytical models for the expected distortion performance of both conventional VQ as well as for channel-optimized VQ. As a practical example, compression of the linear predictive coding parameters in the wideband speech spectrum is considered, with the log spectral distortion as performance metric. The theory is able to correctly predict the channel error rate that is permissible for operation at a particular level of distortion.

Diversity order vs rate in an AWGN channel

We study the diversity order vs rate of an additive white Gaussian noise (AWGN) channel in the whole capacity region. We show that for discrete input as well as for continuous input, Gallager's upper bounds on error probability have exponential diversity in low and high rate region but only subexponential in the mid-rate region. For the best available lower bounds and for the practical codes one observes exponential diversity throughout the capacity region. However we also show that performance of practical codes is close to Gallager's upper bounds and the mid-rate subexponential diversity has a bearing on the performance of the practical codes. Finally we show that the upper bounds with Gaussian input provide good approximation throughout the capacity region even for finite constellation.

Reach task-associated excitatory overdrive of motor cortical neurons following infusion with ALS-CSF

Converging evidence from transgenic animal models of amyotrophic lateral sclerosis (ALS) and human studies suggest alterations in excitability of the motor neurons in ALS. Specifically, in studies on human subjects with ALS the motor cortex was reported to be hyperexcitable. The present study was designed to test the hypothesis that infusion of cerebrospinal fluid from patients with sporadic ALS (ALS-CSF) into the rat brain ventricle can induce hyperexcitability and structural changes in the motor cortex leading to motor dysfunction. A robust model of sporadic ALS was developed experimentally by infusing ALS-CSF into the rat ventricle. The effects of ALS-CSF at the single neuron level were examined by recording extracellular single unit activity from the motor cortex while rats were performing a reach to grasp task. We observed an increase in the firing rate of the neurons of the motor cortex in rats infused with ALS-CSF compared to control groups. This was associated with impairment in a specific component of reach with alterations in the morphological characteristics of the motor cortex. It is likely that the increased cortical excitability observed in the present study could be the result of changes in the intrinsic properties of motor cortical neurons, a dysfunctional inhibitory mechanism and/or an underlying structural change culminating in a behavioral deficit.

Liquid crystal based continuous phase retarder: From optically neutral to a quarter waveplate in 200 microseconds

Liquid crystal variable phase retarders have been incorporated into prototype devices for optical communications system applications, both as endless polarization controllers 1,2,3, and as holographic beam steerers 4. Nematic liquid crystals allow continuous control of the degree of retardation induced at relatively slow switching speeds, while ferroelectric liquid crystal based devices allow fast (sub millisecond) switching, but only between two bistable states. The flexoelectro-optic effect 5,6 in short-pitch chiral nematic liquid crystals allows both fast switching of the optic axis and continuous, electric field dependent control of the degree of rotation of the optic axis. A novel geometry for the flexoelectro-optic effect is presented here, in which the helical axis of the chiral nematic is perpendicular to the cell walls (grandjean texture) and the electric field is applied in the plane of the cell. This facilitates deflection of the optic axis of the uniaxial negatively birefringent material from lying along the direction of propagation to having some component in the polarization plane of the light. The device is therefore optically neutral at zero field for telecommunications wavelengths (1550nm), and allows a continuously variable degree of phase excursion to be induced, up to 2π/3 radians achieved so far in a 40μm thick cell. The retardation has been shown both to appear, on application of the field, and disappear on removal, at speeds of 100-500 μs. The direction of deflection of the optic axis is also dependent on the direction of the field, allowing the possibility, in a converging electrode "cartwheel cell", of endless rotation of the liquid crystal waveplate at a higher rate than achievable through dielectric coupling to plain nematic materials.

Strain Rate Dependence of Plastic Flow in Ce-based Bulk Metallic Glass During Nanoindentation

The strain rate dependence of plastic deformation of Ce60Al15CU10Ni15 bulk metallic glass was studied by nanoindentation. Even though the ratio of room temperature to the glass transition temperature was very high (0.72) for this alloy, the plastic deformation was dominated by shear banding under nanoindentation. The alloy exhibited a critical loading rate dependent serrated flow feature. That is, with increasing loading rate, the alloy exhibited a transition from less prominent serrated flow to pronounced serrated flow during continuous loading but from serrated to smoother flow during stepped loading.

Dasher - A data entry interface using continuous gestures and language models

Existing devices for communicating information to computers are bulky, slow to use, or unreliable. Dasher is a new interface incorporating language modelling and driven by continuous two-dimensional gestures, e.g. a mouse, touchscreen, or eye-tracker. Tests have shown that this device can be used to enter text at a rate of up to 34 words per minute, compared with typical ten-finger keyboard typing of 40-60 words per minute. Although the interface is slower than a conventional keyboard, it is small and simple, and could be used on personal data assistants and by motion-impaired computer users.

Kinetic model of continuous-wave flow chemical lasers

In this paper an analysis of the kinetic theory of the continuous-wave flow chemical lasers(CWFCL) is presented with emphasis being laid on the effects of inhomogeneous broadeningon CWFCL's performance. The results obtained are applicable to the case where laser fre-quency is either coincident or incoincident with that of the eenter of the line shape. This rela-tion has been,compared with that of the rate model in common use. These two models are almostidentical as the broadening parameter η is larger than 1. The smaller the value of η, thegreater the difference between the results of these two models will be. For fixed η, the dif-ferences between fhe results of the two models increase with the increase of the frequencyshift parameter ξ. When η is about less than 0.2. the kinetic model can predict exactly the in-homogeneous broadening effects,while the rate model cannot.

Use of generalised additive models to categorise continuous variables in clinical prediction

13 P.

Evaluation of Fentanyl Disposition and Effects in Newborn Piglets as an Experimental Model for Human Neonates

Background: Fentanyl is widely used off-label in NICU. Our aim was to investigate its cerebral, cardiovascular and pulmonary effects as well as pharmacokinetics in an experimental model for neonates. Methods: Fentanyl (5 mu g/kg bolus immediately followed by a 90 minute infusion of 3 mu g/kg/h) was administered to six mechanically ventilated newborn piglets. Cardiovascular, ventilation, pulmonary and oxygenation indexes as well as brain activity were monitored from T = 0 up to the end of experiments (T = 225-300 min). Also plasma samples for quantification of fentanyl were drawn. Results: A "reliable degree of sedation" was observed up to T = 210-240 min, consistent with the selected dosing regimen and the observed fentanyl plasma levels. Unlike cardiovascular parameters, which were unmodified except for an increasing trend in heart rate, some of the ventilation and oxygenation indexes as well as brain activity were significantly altered. The pulmonary and brain effects of fentanyl were mostly recovered from T = 210 min to the end of experiment. Conclusion: The newborn piglet was shown to be a suitable experimental model for studying fentanyl disposition as well as respiratory and cardiovascular effects in human neonates. Therefore, it could be extremely useful for further investigating the drug behaviour under pathophysiological conditions.

Proposal and validation of methodologies for the categorisation of continuous variables in the development of prediction models

158 p.

Eventos cardíacos decorrentes da infusão contínua de cloridrato de amiodarona: implicações para o enfermeiro

O objeto de estudo são os eventos cardíacos resultantes da infusão contínua de cloridrato de amiodarona em pacientes que evoluíram com fibrilação atrial em pós-operatório de cirurgia cardíaca. Os objetivos foram descrever as características dos pacientes que receberam infusão contínua de cloridrato de amidoarona, apresentar a prevalência de bradicardia e hipotensão encontrada nos pacientes que receberam infusão contínua de cloridrato de amiodarona e discutir as implicações dos achados para a prática dos enfermeiros a partir da prevalência encontrada de bradicardia e hipotensão decorrente da infusão contínua desta substância. Trata-se de um estudo transversal, retrospectivo, documental, por meio de análise de prontuários e avaliação quantitativa dos mesmos. Desenvolvida em uma unidade de pós-operatório de cirurgia cardíaca em um hospital universitário pertencente à rede sentinela no município do Rio de Janeiro. Foi considerado hipotensão em presença de PAS menor que 90 mmHg e bradicardia em presença de frequência cardíaca menor que 60 bpm. As variáveis que caracterizavam a população do estudo e as aferições de pressão arterial e frequência cardíaca foram transcritas para um instrumento de coleta de dados dos anos de 2010 e 2011, gerando 1782 horas de infusão contínua de cloridrato de amiodarona em 27 pacientes cirúrgicos (10,50%). Tratou-se de uma população predominantemente feminina, com idade a cima de 60 anos, período de internação superior a uma semana, apresentava hipertensão arterial prévia (59,26%), era portadora de fibrilação atrial (55,56%) e o diagnóstico cirúrgico de revascularização do miocárdio com circulação extracorpórea foi predominante (70,37%). Os dados mostram que 85,19% dos pacientes eram portadores de pelo menos um fator de risco, 70,37% apresentavam dois fatores de risco e 55,55% apresentavam três fatores de risco para desenvolver fibrilação atrial no pós-operatório de cirurgia cardíaca. Foi encontrada uma prevalência de 85,19% pacientes que apresentaram bradicardia, 66,67% apresentaram hipotensão e 59,26% apresentaram tanto bradicardia como hipotensão. Foram 160 episódios de bradicardia com 6,40 episódios por paciente e 77 episódios de hipotensão com 4,2 por paciente. A bradicardia ocorreu principalmente entre 48 e 72 horas do inicio da infusão. Já a hipotensão aumentou progressivamente nas primeiras 48 horas de infusão. Na presença de bradicardia a intervenção mais frequente foi redução da vazão de amiodarona já na presença de hipotensão, a manutenção de infusão de noradrenalina foi a conduta mais regular. Como estratégia de melhoria para segurança do paciente, foram elaboradas condutas como método de barreira para prevenção de eventos adversos como a bradicardia e hipotensão. Os principais cuidados de enfermagem a serem implementados pelo enfermeiro foram o levantamento de fatores de risco para a fibrilação atrial, a detecção da fibrilação atrial, a manutenção de monitorização cardíaca contínua, aferição horária do ritmo cardíaco e o controle da frequência cardíaca e pressão arterial, objetivando intervir precocemente em presença de hipotensão ou bradicardia.