Histopathology of oligofructose-induced acute laminitis in heifers

Histopathology of the dermo-epidermal junction in the lamellar region of front claws was examined in 6 dairy heifers given an alimentary oligofructose overload and compared with sections from a control group of 6 heifers. Four of the 6 heifers administered oligofructose developed clinical signs of acute laminitis before they were euthanized. Postmortem samples from front claws were processed for histology. Eleven histopathologic characteristics were selected from the existing literature and used in a blinded evaluation of sections. In total, 104 front claw samples, including 8 samples from 2 cows having spontaneously occurring acute laminitis, were evaluated histologically using hematoxylin and eosin as well as periodic acid-Schiff staining. The major morphological features associated with oligofructose-induced acute clinical laminitis were stretching of lamellae, dermal edema, hemorrhage, changes in basal cell morphology, presence of white blood cells in dermis, and signs of basement membrane detachment. Changes at the lamellar junction of claw tissue affected by oligofructose-induced clinical laminitis resembled tissue from the 2 cows suffering from spontaneous acute clinical laminitis, and generally were consistent with existing descriptions of laminitis histopathology. Important exceptions to existing descriptions in the literature were stretching of lamellae and basement membrane changes. Not previously described, we considered these early signs of acute laminitis. In conclusion, this study documents that oligofructose-induced clinical laminitis is associated with histopathological changes at the lamellar interface. A weakened dermo-epidermal junction is a possible intermediate stage in the pathophysiology of bovine sole ulceration at the typical site.

Effect of initial disturbance amplitude in gravity affected jet break-up

The initial disturbance amplitude has an effect on stretching jets that is not observed for capillary jet instability where gravitational acceleration is not significant. For inviscid and viscous fluids, gravity diminishes the effect that the initial amplitude has on jet length and its ability to prevent satellite formation. In stretching jets, not only the dimensionless frequency of the disturbance but also its initial amplitude must be known to properly study their satellite forming nature. Indirect methods of relating the applied disturbance energy to an initial velocity perturbation are not simple when the gravity parameter G is changing. When G A 0, the optimum disturbance frequency Omega(opt) and the initial disturbance amplitude are related, with Omega(opt) proportional to f (G) x In(1 /epsilon(nu)). Results from numerical simulations and experiments are presented here. (c) 2005 Elsevier Ltd. All rights reserved.

Drying process of microcrystalline cellulose studied by attenuated total reflection IR spectroscopy with two-dimensional correlation spectroscopy and principal component analysis

Molecular interactions between microcrystalline cellulose (MCC) and water were investigated by attenuated total reflection infrared (ATR/IR) spectroscopy. Moisture-content-dependent IR spectra during a drying process of wet MCC were measured. In order to distinguish overlapping O–H stretching bands arising from both cellulose and water, principal component analysis (PCA) and, generalized two-dimensional correlation spectroscopy (2DCOS) and second derivative analysis were applied to the obtained spectra. Four typical drying stages were clearly separated by PCA, and spectral variations in each stage were analyzed by 2DCOS. In the drying time range of 0–41 min, a decrease in the broad band around 3390 cm−1 was observed, indicating that bulk water was evaporated. In the drying time range of 49–195 min, decreases in the bands at 3412, 3344 and 3286 cm−1 assigned to the O6H6cdots, three dots, centeredO3′ interchain hydrogen bonds (H-bonds), the O3H3cdots, three dots, centeredO5 intrachain H-bonds and the H-bonds in Iβ phase in MCC, respectively, were observed. The result of the second derivative analysis suggests that water molecules mainly interact with the O6H6cdots, three dots, centeredO3′ interchain H-bonds. Thus, the H-bonding network in MCC is stabilized by H-bonds between OH groups constructing O6H6cdots, three dots, centeredO3′ interchain H-bonds and water, and the removal of the water molecules induces changes in the H-bonding network in MCC.

Solution properties of star and linear poly(N-isopropylacrylamide)

The LCST transitions of novel N-isopropylacrylamide ( NIPAM) star polymers, prepared using the four-armed RAFT agent pentaerythritoltetrakis(3-(S-benzyltrithiocarbonyl) propionate) (PTBTP) and their hydrolyzed linear arms were studied using H-1 NMR, PFG-NMR, and DLS. The aim was to determine the effect of polymer architecture and the presence of end groups derived from RAFT agents on the LCST. The LCST transitions of star PNIPAM were significantly depressed by the presence of the hydrophobic star core and possibly the benzyl end groups. The effect was molecular weight dependent and diminished once the number of repeating units per arm >= 70. The linear PNIPAM exhibited an LCST of 35 degrees C, regardless of molecular weight; the presence of both hydrophilic and hydrophobic end groups after hydrolysis from the star core was suggested to cancel effects on the LCST. A significant decrease in R-H was observed below the LCST for star and linear PNIPAM and was attributed to the formation of n-clusters. Application of a scaling law to the linear PNIPAM data indicated the cluster size n = 6. Tethering to the hydrophobic star core appeared to inhibit n-cluster formation in the lowest molecular weight stars; this may be due to enhanced stretching of the polymer chains, or the presence of larger numbers of n-clusters at temperatures below those measured.

Drop formation and breakup of low viscosity elastic fluids: Effects of molecular weight and concentration

The dynamics of drop formation and pinch-off have been investigated for a series of low viscosity elastic fluids possessing similar shear viscosities, but differing substantially in elastic properties. On initial approach to the pinch region, the viscoelastic fluids all exhibit the same global necking behavior that is observed for a Newtonian fluid of equivalent shear viscosity. For these low viscosity dilute polymer solutions, inertial and capillary forces form the dominant balance in this potential flow regime, with the viscous force being negligible. The approach to the pinch point, which corresponds to the point of rupture for a Newtonian fluid, is extremely rapid in such solutions, with the sudden increase in curvature producing very large extension rates at this location. In this region the polymer molecules are significantly extended, causing a localized increase in the elastic stresses, which grow to balance the capillary pressure. This prevents the necked fluid from breaking off, as would occur in the equivalent Newtonian fluid. Alternatively, a cylindrical filament forms in which elastic stresses and capillary pressure balance, and the radius decreases exponentially with time. A (0+1)-dimensional finitely extensible nonlinear elastic dumbbell theory incorporating inertial, capillary, and elastic stresses is able to capture the basic features of the experimental observations. Before the critical "pinch time" t(p), an inertial-capillary balance leads to the expected 2/3-power scaling of the minimum radius with time: R-min similar to(t(p)-t)(2/3). However, the diverging deformation rate results in large molecular deformations and rapid crossover to an elastocapillary balance for times t>t(p). In this region, the filament radius decreases exponentially with time R-min similar to exp[(t(p)-t)/lambda(1)], where lambda(1) is the characteristic time constant of the polymer molecules. Measurements of the relaxation times of polyethylene oxide solutions of varying concentrations and molecular weights obtained from high speed imaging of the rate of change of filament radius are significantly higher than the relaxation times estimated from Rouse-Zimm theory, even though the solutions are within the dilute concentration region as determined using intrinsic viscosity measurements. The effective relaxation times exhibit the expected scaling with molecular weight but with an additional dependence on the concentration of the polymer in solution. This is consistent with the expectation that the polymer molecules are in fact highly extended during the approach to the pinch region (i.e., prior to the elastocapillary filament thinning regime) and subsequently as the filament is formed they are further extended by filament stretching at a constant rate until full extension of the polymer coil is achieved. In this highly extended state, intermolecular interactions become significant, producing relaxation times far above theoretical predictions for dilute polymer solutions under equilibrium conditions. (C) 2006 American Institute of Physics

Local geometric changes in left ventricular remodeling post-infarction can lead to apparent reduction in scar thickness

Serial reduction in scar thickness has been shown in animal models. We sought whether this reduction in scar thickness may be a result of dilatation of the left ventricle (LV) with stretching and thinning of the wall. Contrast enhanced magnetic resonance imaging (CMRI) was performed to delineate radial scar thickness in 25 patients (age 63±10, 21 men) after myocardial infarction. The LV was divided into 16 segts and the absolute radial scar thickness (ST) and percentage scar to total wall thickness (%ST) were measured. Regional end diastolic (EDV) and end systolic volumes (ESV) of corresponding segments were measured on CMRI. All patients underwent revascularization and serial changes in ST, %ST, and regional volumes were assessed with a mean follow up of 15±5 months. CMRI identified a total of 93 scar segments. An increase in EDV or ESV was associated with a serial reduction inST(versusEDV, r =−0.3, p = 0.01; versusESV, r =−0.3, p = 0.005) and%ST(versusEDV, r =−0.2, p = 0.04; versus ESV, r =−0.3, p = 0.001). For segts associated with a positive increase in EDV (group I) or ESV (group II) there was a significant decrease in ST and %ST, but in those segts with stable EDV (group III) or ESV (group IV) there were no significant changes in ST and %ST (Table).

Effects of cation substitutions on the physical properties of M2M1T2O6 pyroxenes

In this PhD study, the effects of the cation substitutions on the physical properties of pyroxenes have been discussed. The results of this work extend the knowledge on pyroxenes with different chemical compositions. These properties might be used in the development of ceramic pigments, advanced materials and for the mineralogical phase identification. First of all, the crystallographic differences between Ge and Si pyroxenes have been examined. The structure of C2/c Ca rich Ge clinopyroxenes is very close to the low pressure C2/c structural configuration found in Ca-rich Si-pyroxenes. The shear of the unit cell is very similar, and the difference between a Ge end member and the corresponding Si-rich one is less than 1°. Instead, a remarkable difference exists between Ca-poor Si and Ge clinopyroxenes. First, Ca-poor Ge pyroxenes do not display a P21/c symmetry, but retain the C2/c symmetry; second, the observed C2/c structure shows, at room pressure, the configuration with highly kinked tetrahedral chains characteristic of the high pressure C2/c symmetry of Si Ca-poor pyroxenes. In orthopyroxenes, with Pbca symmetry, Ge-pyroxenes have volume larger than Si-pyroxenes. Samples along the system CaCoGe2O6 - CoCoGe2O6 have been synthesized at three different temperatures: 1050 °C, 1200 °C and 1250 °C. The aim of these solid state syntheses was to obtain a solid solution at ambient pressure, since the analogues Si-system needs high pressure. Unfortunately, very limited solution occurs because the structure forms of the two end member (high temperature for CaCoGe2O6 and high pressure CoCoGe2O6) are incompatible. The phase diagram of this system has been sketched and compared to that of Si. The cobalt end member (CoCoGe2O6) is stable at ambient pressure in two symmetries: at 1050 °C C2/c and 1200 °C Pbca. The impurity phase formed during these experiments is cobalt spinel. Raman spectroscopy has been used to investigate the vibrational properties of Ca-pyroxenes CaCoGe2O6, CaMgGe2O6, CaMgSi2O6 and CaCoSi2O6. A comparison between silicate and germanate pyroxenes shows significant changes in peak positions of the corresponding modes caused mainly by the difference of the Ge-Si atomic weight along with the distortion and compression of the coordination polyhedra. Red shift in Raman spectra of germanates has been calculated by a rough scale factor calculated by a simple harmonic oscillator model, considering the different bond lengths for 4-coordinated Si ~ 1.60- 1.65 Å vs Ge–O distance ~1.70 - 1.80 Å. The Raman spectra of CaMgGe2O6 and CaCoGe2O6 have been classified, in analogy with silicate (Wang et al., 2001) counterparts, in different ranges: - R1 (880-640 cm-1): strong T-O stretching modes of Ge and non-bridging O1 and O2 atoms within the GeO4 tetrahedron; - R2 (640-480 cm-1): stretching/bending modes of Ge-Obr-Ge bonds (chain stretching and chain bending); - R4 (480-360 cm-1): O-Ge-O vibrations; - R3 (360-240 cm-1): motions of the cations in M2 and M1 sites correlated with tetrahedral chain motion and tilting tetrahedra; - R5 (below 240 cm-1): lattice modes. The largest shift with respect to CaMgSi2O6 - CaCoSi2O6 is shown by the T-O stretching and chain modes. High-pressure Raman spectroscopy (up to about 8 GPa) on the same samples of Ca-pyroxenes using an ETH-type diamond anvil cell shows no phase transition within the P-ranges investigated, as all the peak positions vary linearly as a function of pressure. Our data confirm previous experimental findings on Si-diopside (Chopelas and Serghiou, 2000). In the investigated samples, all the Raman peaks shift upon compression, but the major changes in wavenumber with pressure are attributed to the chain bending (Ge-Obr-Ge bonds) and tetrahedra stretching modes (Ge-Onbr). Upon compression, the kinking angle, the bond lengths and T-T distances between tetrahedra decrease and consequently the wavenumber of the bending chain mode and tetrahedra stretching mode increases. Ge-pyroxenes show the higher P-induced peak-position shifts, being more compressible than corresponding silicates. The vibrational properties of CaM2+Ge2O6 (M2+ =Mg, Mn, Fe, Co, Ni, Zn) are reported for the first time. The wavenumber of Ge-Obr-Ge bending modes decreases linearly with increasing ionic radius of the M1 cation. No simple correlation has been found with M1 atomic mass or size or crystallographic parameters for the peak at ~850 cm-1 and in the low wavenumber regions. The magnetic properties of the system CaCoSi2O6 - CoCoSi2O6 have been investigated by magnetometry. The join is always characterized by 1 a.p.f.u. of cobalt in M1 site and this causes a pure collinear antiferromagnetic behaviour of the intra-chain superexchange interaction involving Co ions detected in all the measurements, while the magnetic order developed by the cobalt ions in M2 site (intra-chain) is affected by weak ferromagnetism, due to the non-collinearity of their antiferromagnetic interaction. In magnetically ordered systems, this non-collinearity effect promotes a spin canting of anti-parallel aligned magnetic moments and thus is a source of weak ferromagnetic behaviour in an antiferromagnetic. The weak ferromagnetism can be observed only for the samples with Co content higher than 0.5 a.p.f.u. in M2, when the concentration is sufficiently high to create a long range order along the M2 chain which is magnetically independent of M1 chain. The ferromagnetism was detected both in the M(T) at 10 Oe and M(H).

INTERVENÇÕES FISIOTERAPÊUTICAS NUM CONTEXTO LÚDICO JUNTO A CRIANÇAS COM DOENÇAS RESPIRATÓRIAS CRÔNICAS

Verifica-se hoje em dia o aumento da incidência de problemas pulmonares que ocasiona internações hospitalares infantis com maior freqüência. Este projeto baseia-se na visão biopsicossocial da Psicologia da Saúde e leva em conta a valorização de atividades do cotidiano da criança, como o brincar, para sua recuperação. Tem por objetivo principal investigar se a utilização de técnicas interventivas lúdicas em fisioterapia contribui para a melhora dos níveis de oxigenação de crianças asmáticas e por objetivos específicos traçar um breve perfil clínico da criança que procura o Ambulatório de Alergia e Imunologia da Faculdade de Medicina do ABC e verificar a adesão da criança com problemas respiratórios a uma intervenção fisioterapêutica lúdica da criança. A análise qualitativa da intervenção lúdica registra grande envolvimento e participação prazerosa das crianças e ampla aceitação dos pais. Estes resultados sugerem que novas pesquisas sejam realizadas a respeito de intervenções lúdicas em fisioterapia. Utiliza-se de método avaliativo-interventivo quase-experimental. Seus participantes são 58 crianças de ambos os sexos com idade de quatro a 11 anos com as patologias de asma brônquica, bronquite e rinite alérgica, sem a presença da crise. Desenvolve-se por meio de sessão única com cada paciente, com avaliação antes e após da intervenção fisioterápica lúdica por meio das aferições dos sinais vitais, (PA, FC, FR,T°C, incluindo oximetria de pulso e PFE) técnicas de aquecimento, alongamento torácico, fortalecimento abdominal e expansão torácica. Realiza análise qualitativa da responsividade das crianças às técnicas interventivas empregadas no contexto lúdico. Os resultados a respeito do perfil clinico indicam maior incidência de Asma, com 44 casos (75,8620 %), para 11 casos de Rinite (18,9655 %) e apenas três de Bronquite (5,1724 %). Os dados relativos a PA, FC, FR,T°C e ao PFE mostram-se dentro da normalidade. Este estudo não constata diferença significativa em relação ao nível de saturação de O2 após a intervenção lúdica. Quanto à adesão, 55,2 % dos participantes aderiram, sendo que a não adesão deu-se por motivos particulares alegados pelos responsáveis ou indisposição da criança, de dor de cabeça, sonolência e/ou vômito. A análise qualitativa da intervenção lúdica registra grande envolvimento e participação prazerosa das crianças e ampla aceitação dos pais. Estes resultados sugerem que novas pesquisas sejam realizadas a respeito de intervenções lúdicas em fisioterapia.(AU)

Posterior retinal contour in adult human anisomyopia

PURPOSE. It is well documented that myopia is associated with an increase in axial length or, more specifically, in vitreous chamber depth. Whether the transverse dimensions of the eye also increase in myopia is relevant to further understanding of its development. METHODS. The posterior retinal surface was localized in two-dimensional space in both eyes of young adult white and Taiwanese-Chinese iso- and anisomyopes (N = 56), from measured keratometry, A-scan ultrasonography, and central and peripheral refraction (±35°) data, with the aid of a computer modeling program designed for this purpose. Anisomyopes had 2 D or more interocular difference in their refractive errors, with mean values in their more myopic eyes of -5.57 D and in their less myopic eyes of -3.25 D, similar to the means of the two isomyopic groups. The derived retinal contours for the more and less myopic eyes were compared by way of investigating ocular shape changes that accompany myopia, in the posterior region of the vitreous chamber. The presence and size of optic disc crescents were also investigated as an index of retinal stretching in myopia. RESULTS. Relative to the less myopic eyes of anisometropic subjects, the more myopic eyes were more elongated and also distorted into a more prolate shape in both the white and Chinese groups. However, the Chinese eyes showed a greater and more uniform relative expansion of the posterior retinal surface in their more myopic eyes, and this was associated with larger optic disc crescents. The changes in the eyes of whites displayed a nasal-temporal axial asymmetry, reflecting greater enlargement of the nasal retinal sector. CONCLUSIONS. Myopia is associated with increased axial length and a prolate shape. This prolate shape is consistent with the proposed idea that axial and transverse dimensions of the eye are regulated differently. The observations that ocular shape changes are larger but more symmetrical in Chinese eyes than in eyes of whites warrant further investigation.

Mechanical properties of sheet metal under forming conditions

In the bulge test, a sheet metal specimen is clamped over a circular hole in a die and formed into a bulge by the hydraulic pressure on one side of the specirnen. As the unsupported part of the specimen is deformed in this way, its area is increased, in other words, the material is generally stretched and its thickness generally decreased. The stresses causing this stretching action are the membrane stresses in the shell generated by the hydraulic pressure, in the same way as the rubber in a toy balloon is stretched by the membrane stresses caused by the air inside it. The bulge test is a widely used sheet metal test, to determine the "formability" of sheet materials. Research on this forming process (2)-(15)* has hitherto been almost exclusively confined to predicting the behaviour of the bulged specimen through the constitutive equations (stresses and strains in relation to displacements and shapes) and empirical work hardening characteristics of the material as determined in the tension test. In the present study the approach is reversed; the stresses and strains in the specimen are measured and determined from the geometry of the deformed shell. Thus, the bulge test can be used for determining the stress-strain relationship in the material under actual conditions in sheet metal forming processes. When sheet materials are formed by fluid pressure, the work-piece assumes an approximately spherical shape, The exact nature and magnitude of the deviation from the perfect sphere can be defined and measured by an index called prolateness. The distribution of prolateness throughout the workpiece at any particular stage of the forming process is of fundamental significance, because it determines the variation of the stress ratio on which the mode of deformation depends. It is found. that, before the process becomes unstable in sheet metal, the workpiece is exactly spherical only at the pole and at an annular ring. Between the pole and this annular ring the workpiece is more pointed than a sphere, and outside this ring, it is flatter than a sphere. In the forming of sheet materials, the stresses and hence the incremental strains, are closely related to the curvatures of the workpiece. This relationship between geometry and state of stress can be formulated quantitatively through prolateness. The determination of the magnitudes of prolateness, however, requires special techniques. The success of the experimental work is due to the technique of measuring the profile inclination of the meridional section very accurately. A travelling microscope, workshop protractor and surface plate are used for measurements of circumferential and meridional tangential strains. The curvatures can be calculated from geometry. If, however, the shape of the workpiece is expressed in terms of the current radial (r) and axial ( L) coordinates, it is very difficult to calculate the curvatures within an adequate degree of accuracy, owing to the double differentiation involved. In this project, a first differentiation is, in effect, by-passed by measuring the profile inclination directly and the second differentiation is performed in a round-about way, as explained in later chapters. The variations of the stresses in the workpiece thus observed have not, to the knowledge of the author, been reported experimentally. The static strength of shells to withstand fluid pressure and their buckling strength under concentrated loads, both depend on the distribution of the thickness. Thickness distribution can be controlled to a limited extent by changing the work hardening characteristics of the work material and by imposing constraints. A technique is provided in this thesis for determining accurately the stress distribution, on which the strains associated with thinning depend. Whether a problem of controlled thickness distribution is tackled by theory, or by experiments, or by both combined, the analysis in this thesis supplies the theoretical framework and some useful experimental techniques for the research applied to particular problems. The improvement of formability by allowing draw-in can also be analysed with the same theoretical and experimental techniques. Results on stress-strain relationships are usually represented by single stress-strain curves plotted either between one stress and one strain (as in the tension or compression tests) or between the effective stress and effective strain, as in tests on tubular specimens under combined tension, torsion and internal pressure. In this study, the triaxial stresses and strains are plotted simultaneously in triangular coordinates. Thus, both stress and strain are represented by vectors and the relationship between them by the relationship between two vector functions. From the results so obtained, conclusions are drawn on both the behaviour and the properties of the material in the bulge test. The stress ratios are generally equal to the strain-rate ratios (stress vectors collinear with incremental strain vectors) and the work-hardening characteristics, which apply only to the particular strain paths are deduced. Plastic instability of the material is generally considered to have been reached when the oil pressure has attained its maximum value so that further deformation occurs under a constant or lower pressure. It is found that the instability regime of deformation has already occurred long before the maximum pressure is attained. Thus, a new concept of instability is proposed, and for this criterion, instability can occur for any type of pressure growth curves.

The preparation of carbon fibres: a study of the physics and chemistry of the preparation of carbon fibres from acrylic precursors

High strength, high modulus carbon fibres are becoming increasingly important as high performance engineering materials. This thesis describes how they may be prepared by heat treatment from filaments spun from polyacrylonitrile and its copolymers. The chemistry of the first stages of heat treatment is very important in controlling the mechanical properties of the carbonised product. A cyclisation reaction has been found to be responsible for the relatively high thermal stability of pyrolysed polyacrylonitrile, but without oxidation the fibres degrade and fuse. An initial oxidation stage is, therefore, essential to the preparation of fibre of high orientation. The cyclised product of pyrolysis is probably a poly 1,4 dihydropiridine and oxidation converts this to aromatic structures, and cyclised structures containing carbonyl and other oxygenated groups. Oxidation is found to assist the carbon fibre preparation process, by producing a product which condenses at an earlier stage of heat treatment, before fusion can occur. Carbon fibre strength and modulus are dependent upon producing a highly oriented crystal structure. While oxidation of the polymer stabilises the fibre so as to prevent disorientation, further large increases in orientation, with a commensurate improvement in strength and modulus, can be obtained by stretching at temperatures above 1,700 °C. This process is analogous to the way fibre orientation is increased by the stretching of the precursor. A lamellar graphite structure can be created in high temperature fibre, by carefully controlling the degree of oxidation. This type of graphite can produce very high values of Young's modulus. More often, however, graphite fibre has a fibrillar fine structure, which is explicable in terms of continuous graphite ribbons. A ribbon model is the most satisfactory representation of the structure of carbon fibre, as it explains the mechanism of the development of long range order and the variation of Young's modulus with crystalline preferred orientation.

Quantifying short-term dynamics of Parkinson's disease using self-reported symptom data from an internet social network

Background: Parkinson’s disease (PD) is an incurable neurological disease with approximately 0.3% prevalence. The hallmark symptom is gradual movement deterioration. Current scientific consensus about disease progression holds that symptoms will worsen smoothly over time unless treated. Accurate information about symptom dynamics is of critical importance to patients, caregivers, and the scientific community for the design of new treatments, clinical decision making, and individual disease management. Long-term studies characterize the typical time course of the disease as an early linear progression gradually reaching a plateau in later stages. However, symptom dynamics over durations of days to weeks remains unquantified. Currently, there is a scarcity of objective clinical information about symptom dynamics at intervals shorter than 3 months stretching over several years, but Internet-based patient self-report platforms may change this. Objective: To assess the clinical value of online self-reported PD symptom data recorded by users of the health-focused Internet social research platform PatientsLikeMe (PLM), in which patients quantify their symptoms on a regular basis on a subset of the Unified Parkinson’s Disease Ratings Scale (UPDRS). By analyzing this data, we aim for a scientific window on the nature of symptom dynamics for assessment intervals shorter than 3 months over durations of several years. Methods: Online self-reported data was validated against the gold standard Parkinson’s Disease Data and Organizing Center (PD-DOC) database, containing clinical symptom data at intervals greater than 3 months. The data were compared visually using quantile-quantile plots, and numerically using the Kolmogorov-Smirnov test. By using a simple piecewise linear trend estimation algorithm, the PLM data was smoothed to separate random fluctuations from continuous symptom dynamics. Subtracting the trends from the original data revealed random fluctuations in symptom severity. The average magnitude of fluctuations versus time since diagnosis was modeled by using a gamma generalized linear model. Results: Distributions of ages at diagnosis and UPDRS in the PLM and PD-DOC databases were broadly consistent. The PLM patients were systematically younger than the PD-DOC patients and showed increased symptom severity in the PD off state. The average fluctuation in symptoms (UPDRS Parts I and II) was 2.6 points at the time of diagnosis, rising to 5.9 points 16 years after diagnosis. This fluctuation exceeds the estimated minimal and moderate clinically important differences, respectively. Not all patients conformed to the current clinical picture of gradual, smooth changes: many patients had regimes where symptom severity varied in an unpredictable manner, or underwent large rapid changes in an otherwise more stable progression. Conclusions: This information about short-term PD symptom dynamics contributes new scientific understanding about the disease progression, currently very costly to obtain without self-administered Internet-based reporting. This understanding should have implications for the optimization of clinical trials into new treatments and for the choice of treatment decision timescales.

Real and imaginary parts of the vibrational relaxation of acetonitrile in its electrolyte solutions:new results for the dynamics of solvent molecules

Isotropic scattering Raman spectra of liquid acetonitrile (AN) solutions of LiBF4 and NaI at various temperatures and concentrations have been investigated. For the first time imaginary as well as real parts of the solvent vibrational correlation functions have been extracted from the spectra. Such imaginary parts are currently an important component of modern theories of vibrational relaxation in liquids. This investigation thus provides the first experimental data on imaginary parts of a correlation function in AN solutions. Using the fitting algorithm we recently developed, statistically confident models for the Raman spectra were deduced. The parameters of the band shapes, with an additional correction, of the ν2 AN vibration (CN stretching), together with their confidence intervals are also reported for the first time. It is shown that three distinct species, with lifetimes greater than ∼10−13 s, of the AN molecules can be detected in solutions containing Li+ and Na+. These species are attributed to AN molecules directly solvating cations; the single oriented and polarised molecules interleaving the cation and anion of a Solvent Shared Ion Pair (SShIP); and molecules solvating anions. These last are considered to be equivalent to the next layer of solvent molecules, because the CN end of the molecule is distant from the anion and thus less affected by the ionic charge compared with the anion situation. Calculations showed that at the concentrations employed, 1 and 0.3 M, there were essentially no other solvent molecules remaining that could be considered as bulk solvent. Calculations also showed that the internuclear distance in these solutions supported the proposal that the ionic entity dominating in solution was the SShIP, and other evidence was adduced that confirmed the absence of Contact Ion Pairs at these concentrations. The parameters of the shape of the vibrational correlation functions of all three species are reported. The parameters of intramolecular anharmonic coupling between the potential surfaces in AN and the dynamics of the intermolecular environment fluctuations and intermolecular energy transfer are presented. These results will assist investigations made at higher and lower concentrations, when additional species and interactions with AN molecules will be present.

Tensile properties of as fabricated, aged, and stretched SiC whisker and particle reinforced 2009 aluminium alloy

Tensile tests were carried out using specimens of 2009 aluminium alloy reinforced by either SiC whiskers or particles. The size distributions of the whiskers and particles in the matrix were obtained by image analysis. It was found that failure was a result of uniform void nucleation and coalescence in the as fabricated composites, or a result of fast crack propagation initiated by a flaw developed at clusters of SiC in the aged or stretched and aged composites. The strengths of the as fabricated composites were estimated based on the results of image analysis using continuum mechanics and dislocation theories. The estimation indicated that the tensile strengths are largely contributed to by composite strengthening, supplemented by residual dislocation strengthening and work hardening. Owing to the flaw controlled failure, the tensile strengths of the aged or stretched and aged composites were independent of aging time, aging temperature, and the amount of stretching. The elastic moduli of the composites were estimated using the Halpin-Tsai model and a good correlation was found between the measured and estimated moduli. © 1996 The Institute of Materials.

Computational modeling of biodegradable starch based polymer composites

Purpose. The goal of this study is to improve the favorable molecular interactions between starch and PPC by addition of grafting monomers MA and ROM as compatibilizers, which would advance the mechanical properties of starch/PPC composites. ^ Methodology. DFT and semi-empirical methods based calculations were performed on three systems: (a) starch/PPC, (b) starch/PPC-MA, and (c) starch-ROM/PPC. Theoretical computations involved the determination of optimal geometries, binding-energies and vibrational frequencies of the blended polymers. ^ Findings. Calculations performed on five starch/PPC composites revealed hydrogen bond formation as the driving force behind stable composite formation, also confirmed by the negative relative energies of the composites indicating the existence of binding forces between the constituent co-polymers. The interaction between starch and PPC is also confirmed by the computed decrease in stretching CO and OH group frequencies participating in hydrogen bond formation, which agree qualitatively with the experimental values. ^ A three-step mechanism of grafting MA on PPC was proposed to improve the compatibility of PPC with starch. Nine types of 'blends' produced by covalent bond formation between starch and MA-grafted PPC were found to be energetically stable, with blends involving MA grafted at the 'B' and 'C' positions of PPC indicating a binding-energy increase of 6.8 and 6.2 kcal/mol, respectively, as compared to the non-grafted starch/PPC composites. A similar increase in binding-energies was also observed for three types of 'composites' formed by hydrogen bond formation between starch and MA-grafted PPC. ^ Next, grafting of ROM on starch and subsequent blend formation with PPC was studied. All four types of blends formed by the reaction of ROM-grafted starch with PPC were found to be more energetically stable as compared to the starch/PPC composite and starch/PPC-MA composites and blends. A blend of PPC and ROM grafted at the ' a&d12; ' position on amylose exhibited a maximal increase of 17.1 kcal/mol as compared with the starch/PPC-MA blend. ^ Conclusions. ROM was found to be a more effective compatibilizer in improving the favorable interactions between starch and PPC as compared to MA. The ' a&d12; ' position was found to be the most favorable attachment point of ROM to amylose for stable blend formation with PPC.^