The Selection of Azeotropes at Ambient Pressure Drying of Aerogels

The representation of phase states in the multicomponent systems by graphical images is used for estimation of the LV (xL = xV) azeotrope influence on SLV and L = V equilibria. These theoretical investigations occurred from complications arising at an ambient pressure drying (APD) synthesis of transparent and crackfree bulk silica aerogels. During the empiric selection of azeotropic mixtures, the negative azeotropes advantage over positive ones for this goal is determined and substantiated in theory. As shown, the forecast must base not only on the critical points of components (L = V), in which liquid and vapour become indistinguishable, but also on the triple points of components (SLV–crystal—liquid—vapour). Using the P—T—x phase diagrams, the prediction of ways to reach a supercritical region at the ambient pressure is done. A good agreement between the theoretical results and experimental data is revealed.Представлення фазових рівноваг у багатокомпонентних системах методою графічного зображення використовувалося для оцінки впливу азеотропу LV (xL = xV) на рівноваги SLV та L = V. Дані теоретичні дослідження виконувалися через виникнення ускладнень при синтезі прозорих і бездефектних кремнійових аероґелів способом атмосферного сушіння (APD). При емпіричному відборі азеотропних сумішей було визначено і теоретично обґрунтовано перевагу використання неґативних азеотропів над позитивними задля зазначеної мети. Показано, що прогноза має бути основаною не лише на критичних точках компонентів L = V, в яких рідина і пар стають нерозрізненними, але й на потрійних точках компонентів SLV (кристал—рідина—пар). У даній роботі з використанням P—T—x-фазових діяграм показано можливість досягнення надкритичної области за атмосферного тиску. Виявлено хорошу відповідність між теоретичними та експериментальними результатами.Представление фазовых равновесий в многокомпонентных системах методом графического изображения использовано для оценки влияния азеотропа LV (xL = xV) на равновесия SLV и L = V. Данные теоретические исследования выполнялись по причине возникновения сложностей при синтезе прозрачных и бездефектных кремниевых аэрогелей способом атмосферной сушки (APD). При эмпирическом отборе азеотропных смесей определено и теоретически обосновано преимущество использования негативных азеотропов над позитивными для этой цели. Показано, что прогноз должен быть основан не только на критических точках компонентов L = V, в которых жидкость и пар становятся неразличимыми, но и на тройных точках компонентов SLV (кристалл—жидкость—пар). В данной работе с использованием P—T—x-фазовых диаграмм показана возможность достижения сверхкритической области при атмосферном давлении. Обнаружено хорошее соответствие между теоретическими и экспериментальными результатами

The Debye-Waller Factor in solid 3He and 4He

The Debye-Waller factor and the mean-squared displacement from lattice sites for solid 3He and 4He were calculated with Path Integral Monte Carlo at temperatures between 5 K and 35 K, and densities between 38 nm^(-3) and 67 nm^(-3). It was found that the mean-squared displacement exhibits finite-size scaling consistent with a crossover between the quantum and classical limits of N^(-2/3) and N^(-1/3), respectively. The temperature dependence appears to be T^3, different than expected from harmonic theory. An anisotropic k^4 term was also observed in the Debye-Waller factor, indicating the presence of non-Gaussian corrections to the density distribution around lattice sites. Our results, extrapolated to the thermodynamic limit, agree well with recent values from scattering experiments.Comment: 5 figure

Assessment of various continual reassessment method models for dose-escalation phase 1 oncology clinical trials : using real clinical data and simulation studies

Background The continual reassessment method (CRM) identifies the maximum tolerated dose (MTD) more efficiently and identifies the true MTD more frequently compared to standard methods such as the 3 + 3 method. An initial estimate of the dose-toxicity relationship (prior skeleton) is required, and there is limited guidance on how to select this. Previously, we compared the CRM with six different skeletons to the 3 + 3 method by conducting post-hoc analysis on a phase 1 oncology study (AZD3514), each CRM model reduced the number of patients allocated to suboptimal and toxic doses. This manuscript extends this work by assessing the ability of the 3 + 3 method and the CRM with different skeletons in determining the true MTD of various “true” dose-toxicity relationships. Methods One thousand studies were simulated for each “true” dose toxicity relationship considered, four were based on clinical trial data (AZD3514, AZD1208, AZD1480, AZD4877), and four were theoretical. The 3 + 3 method and 2-stage extended CRM with six skeletons were applied to identify the MTD, where the true MTD was considered as the largest dose where the probability of experiencing a dose limiting toxicity (DLT) is ≤33%. Results For every true dose-toxicity relationship, the CRM selected the MTD that matched the true MTD in a higher proportion of studies compared to the 3 + 3 method. The CRM overestimated the MTD in a higher proportion of simulations compared to the 3 + 3 method. The proportion of studies where the correct MTD was selected varied considerably between skeletons. For some true dose-toxicity relationships, some skeletons identified the true MTD in a higher proportion of scenarios compared to the skeleton that matched the true dose-toxicity relationship. Conclusion Through simulation, the CRM generally outperformed the 3 + 3 method for the clinical and theoretical true dose-toxicity relationships. It was observed that accurate estimates of the true skeleton do not always outperform a generic skeleton, therefore the application of wide confidence intervals may enable a generic skeleton to be used. Further work is needed to determine the optimum skeleton

NOx and O3 above a tropical rainforest: an analysis with a global and box model

A cross-platform field campaign, OP3, was conducted in the state of Sabah in Malaysian Borneo between April and July of 2008. Among the suite of observations recorded, the campaign included measurements of NOx and O3 – crucial outputs of any model chemistry mechanism. We describe the measurements of these species made from both the ground site and aircraft. We then use the output from two resolutions of the chemistry transport model p-TOMCAT to illustrate the ability of a global model chemical mechanism to capture the chemistry at the rainforest site. The basic model performance is good for NOx and poor for ozone. A box model containing the same chemical mechanism is used to explore the results of the global model in more depth and make comparisons between the two. Without some parameterization of the nighttime boundary layer – free troposphere mixing (i.e. the use of a dilution parameter), the box model does not reproduce the observations, pointing to the importance of adequately representing physical processes for comparisons with surface measurements. We conclude with a discussion of box model budget calculations of chemical reaction fluxes, deposition and mixing, and compare these results to output from p-TOMCAT. These show the same chemical mechanism behaves similarly in both models, but that emissions and advection play particularly strong roles in influencing the comparison to surface measurements

Atenolol versus losartan in children and young adults with Marfan's syndrome

BACKGROUND : Aortic-root dissection is the leading cause of death in Marfan's syndrome. Studies suggest that with regard to slowing aortic-root enlargement, losartan may be more effective than beta-blockers, the current standard therapy in most centers. METHODS : We conducted a randomized trial comparing losartan with atenolol in children and young adults with Marfan's syndrome. The primary outcome was the rate of aortic-root enlargement, expressed as the change in the maximum aortic-root-diameter z score indexed to body-surface area (hereafter, aortic-root z score) over a 3-year period. Secondary outcomes included the rate of change in the absolute diameter of the aortic root; the rate of change in aortic regurgitation; the time to aortic dissection, aortic-root surgery, or death; somatic growth; and the incidence of adverse events. RESULTS : From January 2007 through February 2011, a total of 21 clinical centers enrolled 608 participants, 6 months to 25 years of age (mean [+/- SD] age, 11.5 +/- 6.5 years in the atenolol group and 11.0 +/- 6.2 years in the losartan group), who had an aorticroot z score greater than 3.0. The baseline-adjusted rate of change (+/- SE) in the aortic-root z score did not differ significantly between the atenolol group and the losartan group (-0.139 +/- 0.013 and -0.107 +/- 0.013 standard-deviation units per year, respectively; P = 0.08). Both slopes were significantly less than zero, indicating a decrease in the degree of aortic-root dilatation relative to body-surface area with either treatment. The 3-year rates of aortic-root surgery, aortic dissection, death, and a composite of these events did not differ significantly between the two treatment groups. CONCLUSIONS : Among children and young adults with Marfan's syndrome who were randomly assigned to losartan or atenolol, we found no significant difference in the rate of aorticroot dilatation between the two treatment groups over a 3-year period

Probing Transport Theories via Two-Proton Source Imaging

Imaging technique is applied to two-proton correlation functions to extract quantitative information about the space-time properties of the emitting source and about the fraction of protons that can be attributed to fast emission mechanisms. These new analysis techniques resolve important ambiguities that bedeviled prior comparisons between measured correlation functions and those calculated by transport theory. Quantitative comparisons to transport theory are presented here. The results of the present analysis differ from those reported previously for the same reaction systems. The shape of the two-proton emitting sources are strongly sensitive to the details about the in-medium nucleon-nucleon cross sections and their density dependence.Comment: 23 pages, 11 figures. Figures are in GIF format. If you need postscript format, please contact: [email protected]

Reversible maps and composites of involutions in groups of piecewise linear homeomorphisms of the real line

An element of a group is reversible if it is conjugate to its own inverse, and it is strongly reversible if it is conjugate to its inverse by an involution. A group element is strongly reversible if and only if it can be expressed as a composite of two involutions. In this paper the reversible maps, the strongly reversible maps, and those maps that can be expressed as a composite of involutions are determined in certain groups of piecewise linear homeomorphisms of the real line

High-precision calculations of van der Waals coefficients for heteronuclear alkali-metal dimers

Van der Waals coefficients for the heteronuclear alkali-metal dimers of Li, Na, K, Rb, Cs, and Fr are calculated using relativistic ab initio methods augmented by high-precision experimental data. We argue that the uncertainties in the coefficients are unlikely to exceed about 1%.Comment: 11 pages, 2 figs, graphicx.st

Charge order and low frequency spin dynamics in lanthanum cuprates revealed by Nuclear Magnetic Resonance

We report detailed 17O, 139La, and 63Cu Nuclear Magnetic Resonance (NMR) and Nuclear Quadrupole Resonance (NQR) measurements in a stripe ordered La1.875Ba0.125CuO4 single crystal and in oriented powder samples of La1.8-xEu0.2SrxCuO4. We observe a partial wipeout of the 17O NMR intensity and a simultaneous drop of the 17O electric field gradient (EFG) at low temperatures where the spin stripe order sets in. In contrast, the 63Cu intensity is completely wiped out at the same temperature. The drop of the 17O quadrupole frequency is compatible with a charge stripe order. The 17O spin lattice relaxation rate shows a peak similar to that of the 139La, which is of magnetic origin. This peak is doping dependent and is maximal at x ~ 1/8.Comment: submitted to European Physical Journal Special Topic

Plasmonic excitations in noble metals: The case of Ag

The delicate interplay between plasmonic excitations and interband transitions in noble metals is described by means of {\it ab initio} calculations and a simple model in which the conduction electron plasmon is coupled to the continuum of electron-hole pairs. Band structure effects, specially the energy at which the excitation of the $d$-like bands takes place, determine the existence of a subthreshold plasmonic mode, which manifests itself in Ag as a sharp resonance at 3.8 eV. However, such a resonance is not observed in the other noble metals. Here, this different behavior is also analyzed and an explanation is provided.Comment: 9 pages, 8 figure