Use of in situ FT-Raman spectroscopy to study the kinetics of the transformation of carbamazepine polymorphs

The solid-state transformation of carbamazepine from form III to form I was examined by Fourier Transform Raman spectroscopy. Using a novel environmental chamber, the isothermal conversion was monitored in situ at 130◦C, 138◦C, 140◦C and 150◦C. The rate of transformation was monitored by taking the relative intensities of peaks arising from two C H bending modes; this approach minimised errors due to thermal artefacts and variations in power intensities or scattering efficiencies from the samples in which crystal habit changed from a characteristic prism morphology (form III) to whiskers (form I). The solid-state transformation at the different temperatures was fitted to various solid-state kinetic models of which four gave good fits, thus indicating the complexity of the process which is known to occur via a solid–gas–solid mechanism. Arrhenius plots from the kinetic models yielded activation energies from 344 kJ mol−1 to 368 kJ mol−1 for the transformation. The study demonstrates the value of a rapid in situ analysis of drug polymorphic type which can be of value for at-line in-process control.

Optimal linearization trajectories for tangent linear models

We examine differential equations where nonlinearity is a result of the advection part of the total derivative or the use of quadratic algebraic constraints between state variables (such as the ideal gas law). We show that these types of nonlinearity can be accounted for in the tangent linear model by a suitable choice of the linearization trajectory. Using this optimal linearization trajectory, we show that the tangent linear model can be used to reproduce the exact nonlinear error growth of perturbations for more than 200 days in a quasi-geostrophic model and more than (the equivalent of) 150 days in the Lorenz 96 model. We introduce an iterative method, purely based on tangent linear integrations, that converges to this optimal linearization trajectory. The main conclusion from this article is that this iterative method can be used to account for nonlinearity in estimation problems without using the nonlinear model. We demonstrate this by performing forecast sensitivity experiments in the Lorenz 96 model and show that we are able to estimate analysis increments that improve the two-day forecast using only four backward integrations with the tangent linear model. Copyright © 2011 Royal Meteorological Society

Mountain waves in two-layer sheared flows: Critical-level effects, wave reflection, and drag enhancement

Internal gravity waves generated in two-layer stratified shear flows over mountains are investigated here using linear theory and numerical simulations. The impact on the gravity wave drag of wind profiles with constant unidirectional or directional shear up to a certain height and zero shear above, with and without critical levels, is evaluated. This kind of wind profile, which is more realistic than the constant shear extending indefinitely assumed in many analytical studies, leads to important modifications in the drag behavior due to wave reflection at the shear discontinuity and wave filtering by critical levels. In inviscid, nonrotating, and hydrostatic conditions, linear theory predicts that the drag behaves asymmetrically for backward and forward shear flows. These differences primarily depend on the fraction of wavenumbers that pass through their critical level before they are reflected by the shear discontinuity. If this fraction is large, the drag variation is not too different from that predicted for an unbounded shear layer, while if it is small the differences are marked, with the drag being enhanced by a considerable factor at low Richardson numbers (Ri). The drag may be further enhanced by nonlinear processes, but its qualitative variation for relatively low Ri is essentially unchanged. However, nonlinear processes seem to interact constructively with shear, so that the drag for a noninfinite but relatively high Ri is considerably larger than the drag without any shear at all.

Development of biomimetic squid-inspired suckers

Biomechanical properties of squid suckers were studied to provide inspiration for the development of sucker artefacts for a robotic octopus. Mechanical support of the rings found inside squid suckers was studied by bending tests. Tensile tests were carried out to study the maximum possible sucking force produced by squid suckers based on the strength of sucker stalks, normalized by the sucking areas. The squid suckers were also directly tested to obtain sucking forces by a special testing arrangement. Inspired by the squid suckers, three types of sucker artefacts were developed for the arm skin of an octopus inspired robot. The first sucker artefact made of knitted nylon sheet reinforced silicone rubber has the same shape as the squid suckers. Like real squid suckers, this type of artefact also has a stalk that is connected to the arm skin and a ring to give radial support.The second design is a straight cylindrical structure with uniform wall thickness made of silicone rubber. One end of the cylinder is directly connected to the arm skin and the other end is open. The final design of the sucker has a cylindrical base and a concave meniscus top. The meniscus was formed naturally using the surface tension of silicone gel, which leads to a higher level of the liquid around the edge of a container. The wall thickness decreases towards the tip of the sucker opening. Sucking forces of all three types of sucker artefacts were measured. Advantages and isadvantages of each sucker type were discussed. The final design of suckers has been implemented to the arm skin prototypes.

Consumption and social identity: evidence from India

We examine spending on consumption items which have signaling value in social interactions across groups with distinctive social identities in India, where social identities are defined by caste and religious affiliations. Using nationally representative micro data on household consumption expenditures, we find that disadvantaged caste groups such as Other Backward Castes spend 8 percent more on visible consumption than Brahmin and High Caste groups while social groups such as Muslims spend 14 percent less, after controlling for differences in permanent income, household assets and household demographic composition. The differences across social groups are significant and robust and these differences persist within different sub populations. We find that the higher spending of OBC households on visible consumption is diverted from education spending, while Muslim households divert spending from visible consumption and education towards greater food spending. Additionally, we find that these consumption patterns can be partly explained as a result of the status signaling nature of the consumption items. We also discuss alternative sources of differences in consumption patterns across groups which stem from religious observance.

Direct observation of membrane insertion by enveloped virus matrix proteins by phosphate displacement

Enveloped virus release is driven by poorly understood proteins that are functional analogs of the coat protein assemblies that mediate intracellular vesicle trafficking. We used differential electron density mapping to detect membrane integration by membrane-bending proteins from five virus families. This demonstrates that virus matrix proteins replace an unexpectedly large portion of the lipid content of the inner membrane face, a generalized feature likely to play a role in reshaping cellular membranes.

Transition from an anti-phase error-correction-mode to a synchronization mode in the mutual hand tracking

Proactive motion in hand tracking and in finger bending, in which the body motion occurs prior to the reference signal, was reported by the preceding researchers when the target signals were shown to the subjects at relatively high speed or high frequencies. These phenomena indicate that the human sensory-motor system tends to choose an anticipatory mode rather than a reactive mode, when the target motion is relatively fast. The present research was undertaken to study what kind of mode appears in the sensory-motor system when two persons were asked to track the hand position of the partner with each other at various mean tracking frequency. The experimental results showed a transition from a mutual error-correction mode to a synchronization mode occurred in the same region of the tracking frequency with that of the transition from a reactive error-correction mode to a proactive anticipatory mode in the mechanical target tracking experiments. Present research indicated that synchronization of body motion occurred only when both of the pair subjects operated in a proactive anticipatory mode. We also presented mathematical models to explain the behavior of the error-correction mode and the synchronization mode.

Ozone database in support of CMIP5 simulations: results and corresponding radiative forcing

A continuous tropospheric and stratospheric vertically resolved ozone time series, from 1850 to 2099, has been generated to be used as forcing in global climate models that do not include interactive chemistry. A multiple linear regression analysis of SAGE I+II satellite observations and polar ozonesonde measurements is used for the stratospheric zonal mean dataset during the well-observed period from 1979 to 2009. In addition to terms describing the mean annual cycle, the regression includes terms representing equivalent effective stratospheric chlorine (EESC) and the 11-yr solar cycle variability. The EESC regression fit coefficients, together with pre-1979 EESC values, are used to extrapolate the stratospheric ozone time series backward to 1850. While a similar procedure could be used to extrapolate into the future, coupled chemistry climate model (CCM) simulations indicate that future stratospheric ozone abundances are likely to be significantly affected by climate change, and capturing such effects through a regression model approach is not feasible. Therefore, the stratospheric ozone dataset is extended into the future (merged in 2009) with multimodel mean projections from 13 CCMs that performed a simulation until 2099 under the SRES (Special Report on Emission Scenarios) A1B greenhouse gas scenario and the A1 adjusted halogen scenario in the second round of the Chemistry-Climate Model Validation (CCMVal-2) Activity. The stratospheric zonal mean ozone time series is merged with a three-dimensional tropospheric data set extracted from simulations of the past by two CCMs (CAM3.5 and GISSPUCCINI)and of the future by one CCM (CAM3.5). The future tropospheric ozone time series continues the historical CAM3.5 simulation until 2099 following the four different Representative Concentration Pathways (RCPs). Generally good agreement is found between the historical segment of the ozone database and satellite observations, although it should be noted that total column ozone is overestimated in the southern polar latitudes during spring and tropospheric column ozone is slightly underestimated. Vertical profiles of tropospheric ozone are broadly consistent with ozonesondes and in-situ measurements, with some deviations in regions of biomass burning. The tropospheric ozone radiative forcing (RF) from the 1850s to the 2000s is 0.23Wm−2, lower than previous results. The lower value is mainly due to (i) a smaller increase in biomass burning emissions; (ii) a larger influence of stratospheric ozone depletion on upper tropospheric ozone at high southern latitudes; and possibly (iii) a larger influence of clouds (which act to reduce the net forcing) compared to previous radiative forcing calculations. Over the same period, decreases in stratospheric ozone, mainly at high latitudes, produce a RF of −0.08Wm−2, which is more negative than the central Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (AR4) value of −0.05Wm−2, but which is within the stated range of −0.15 to +0.05Wm−2. The more negative value is explained by the fact that the regression model simulates significant ozone depletion prior to 1979, in line with the increase in EESC and as confirmed by CCMs, while the AR4 assumed no change in stratospheric RF prior to 1979. A negative RF of similar magnitude persists into the future, although its location shifts from high latitudes to the tropics. This shift is due to increases in polar stratospheric ozone, but decreases in tropical lower stratospheric ozone, related to a strengthening of the Brewer-Dobson circulation, particularly through the latter half of the 21st century. Differences in trends in tropospheric ozone among the four RCPs are mainly driven by different methane concentrations, resulting in a range of tropospheric ozone RFs between 0.4 and 0.1Wm−2 by 2100. The ozone dataset described here has been released for the Coupled Model Intercomparison Project (CMIP5) model simulations in netCDF Climate and Forecast (CF) Metadata Convention at the PCMDI website (http://cmip-pcmdi.llnl.gov/).

Choosing the most suitable analogue redesign method for forward-type digital power converters

This work proposes a method to objectively determine the most suitable analogue redesign method for forward type converters under digital voltage mode control. Particular emphasis is placed on determining the method which allows the highest phase margin at the particular switching and crossover frequencies chosen by the designer. It is shown that at high crossover frequencies with respect to switching frequency, controllers designed using backward integration have the largest phase margin; whereas at low crossover frequencies with respect to switching frequency, controllers designed using bilinear integration have the largest phase margins. An accurate model of the power stage is used for simulation, and experimental results from a Buck converter are collected. The performance of the digital controllers is compared to that of the equivalent analogue controller both in simulation and experiment. Excellent correlation between the simulation and experimental results is presented. This work will allow designers to confidently choose the analogue redesign method which yields the greater phase margin for their application.

Should kids pay their own way?

Children are expensive to raise. Ensuring that they are raised such that they are able to lead a minimally decent life costs time and money, and lots of both. Who is responsible for bearing the costs of the things that children are undoubtedly owed? This is a question that has received comparatively little scrutiny from political philosophers, despite children being such a drain on public and private finances alike. To the extent that there is a debate, two main views can be identified. The Parents Pay view says that parents, responsible for the existence of the costs, must foot the bill. The Society Pays view says that a next generation is a benefit to all, and so to allow parents to foot the bill alone is the worst kind of free-riding. In this paper, I introduce a third potentially liable party currently missing from the debate: children themselves. On my backward-looking view, we are entitled to ask people to contribute to the raising of children on the basis that they have benefited from being raised themselves.

Crooks' fluctuation theorem for a process on a two dimensional fluid field

We investigate the behavior of a two-dimensional inviscid and incompressible flow when pushed out of dynamical equilibrium. We use the two-dimensional vorticity equation with spectral truncation on a rectangular domain. For a sufficiently large number of degrees of freedom, the equilibrium statistics of the flow can be described through a canonical ensemble with two conserved quantities, energy and enstrophy. To perturb the system out of equilibrium, we change the shape of the domain according to a protocol, which changes the kinetic energy but leaves the enstrophy constant. We interpret this as doing work to the system. Evolving along a forward and its corresponding backward process, we find numerical evidence that the distributions of the work performed satisfy the Crooks relation. We confirm our results by proving the Crooks relation for this system rigorously.

Tracing troposphere-to-stratosphere transport above a mid-latitude deep convective system

Within the project SPURT (trace gas measurements in the tropopause region) a variety of trace gases have been measured in situ in order to investigate the role of dynamical and chemical processes in the extra-tropical tropopause region. In this paper we report on a flight on 10 November 2001 leading from Hohn, Germany (52�N) to Faro, Portugal (37�N) through a strongly developed deep stratospheric intrusion. This streamer was associated with a large convective system over the western Mediterranean with potentially significant troposphere-to-stratosphere transport. Along major parts of the flight we measured unexpectedly high NOy mixing ratios. Also H2O mixing ratios were significantly higher than stratospheric background levels confirming the extraordinary chemical signature of the probed air masses in the interior of the streamer. Backward trajectories encompassing the streamer enable to analyze the origin and physical characteristics of the air masses and to trace troposphere-to-stratosphere transport. Near the western flank of the streamer features caused by long range transport, such as tropospheric filaments characterized by sudden drops in the O3 and NOy mixing ratios and enhanced CO and H2O can be reconstructed in great detail using the reverse domain filling technique. These filaments indicate a high potential for subsequent mixing with the stratospheric air. At the south-western edge of the streamer a strong gradient in the NOy and the O3 mixing ratios coincides very well with a sharp gradient in potential vorticity in the ECMWF fields. In contrast, in the interior of the streamer the observed highly elevated NOy and H2O mixing ratios up to a potential temperature level of 365K and potential vorticity values of maximum 10 PVU cannot be explained in terms of resolved troposphere-to-stratosphere transport along the backward trajectories. Also mesoscale simulations with a High Resolution Model reveal no direct evidence for convective H2O injection up to this level. Elevated H2O mixing ratios in the ECMWF and HRM are seen only up to about tropopause height at 340 hPa and 270 hPa, respectively, well below flight altitude of about 200 hPa. However, forward tracing of the convective influence as identified by satellite brightness temperature measurements and counts of lightning strokes shows that during this part of the flight the aircraft was closely following the border of an air mass which was heavily impacted by convective activity over Spain and Algeria. This is evidence that deep convection at mid-latitudes may have a large impact on the tracer distribution of the lowermost stratosphere reaching well above the thunderstorms anvils as claimed by recent studies using cloud-resolving models.

Transport timescales and tracer properties in the extratropical UTLS

A comprehensive evaluation of seasonal backward trajectories initialized in the northern hemisphere lowermost stratosphere (LMS) has been performed to investigate the factors that determine the temporal and spatial structure of troposphere-to-stratosphere-transport (TST) and it's impact on the LMS. In particular we explain the fundamental role of the transit time since last TST (tTST) for the chemical composition of the LMS. According to our results the structure of the LMS can be characterized by a layer with tTST<40 days forming a narrow band around the local tropopause. This layer extends about 30 K above the local dynamical tropopause, corresponding to the extratropical tropopause transition layer (ExTL) as identified by CO. The LMS beyond this layer shows a relatively well defined separation as marked by an aprupt transition to longer tTST indicating less frequent mixing and a smaller fraction of tropospheric air. Thus the LMS constitutes a region of two well defined regimes of tropospheric influence. These can be characterized mainly by different transport times from the troposphere and different fractions of tropospheric air. Carbon monoxide (CO) mirrors this structure of tTST due to it's finite lifetime on the order of three months. Water vapour isopleths, on the other hand, do not uniquely indicate TST and are independent of tTST, but are determined by the Lagrangian Cold Point (LCP) of air parcels. Most of the backward trajectories from the LMS experienced their LCP in the tropics and sub-tropics, and TST often occurs 20 days after trajectories have encountered their LCP. Therefore, ExTL properties deduced from CO and H2O provide totally different informations on transport and particular TST for the LMS.

GSHMC: an efficient method for molecular simulation

The hybrid Monte Carlo (HMC) method is a popular and rigorous method for sampling from a canonical ensemble. The HMC method is based on classical molecular dynamics simulations combined with a Metropolis acceptance criterion and a momentum resampling step. While the HMC method completely resamples the momentum after each Monte Carlo step, the generalized hybrid Monte Carlo (GHMC) method can be implemented with a partial momentum refreshment step. This property seems desirable for keeping some of the dynamic information throughout the sampling process similar to stochastic Langevin and Brownian dynamics simulations. It is, however, ultimate to the success of the GHMC method that the rejection rate in the molecular dynamics part is kept at a minimum. Otherwise an undesirable Zitterbewegung in the Monte Carlo samples is observed. In this paper, we describe a method to achieve very low rejection rates by using a modified energy, which is preserved to high-order along molecular dynamics trajectories. The modified energy is based on backward error results for symplectic time-stepping methods. The proposed generalized shadow hybrid Monte Carlo (GSHMC) method is applicable to NVT as well as NPT ensemble simulations.