693 research outputs found
Controlling the crystal polymorph by exploiting the time dependence of nucleation rates
Most substances can crystallise into two or more different crystal lattices,
called polymorphs. Despite this, there are no systems in which we can
quantitatively predict the probability of one competing polymorph forming,
instead of the other. We address this problem using large scale (hundreds of
events) studies of the competing nucleation of the alpha and gamma polymorphs
of glycine. In situ Raman spectroscopy is used to identify the polymorph of
each crystal. We find that the nucleation kinetics of the two polymorphs is
very different. Nucleation of the alpha polymorph starts off slowly but
accelerates, while nucleation of the gamma polymorph starts off fast but then
slows. We exploit this difference to increase the purity with which we obtain
the gamma polymorph by a factor of ten. The statistics of the nucleation of
crystals is analogous to that of human mortality, and using a result from
medical statistics we show that conventional nucleation data can say nothing
about what, if any, are the correlations between competing nucleation
processes. Thus we can show that, with data of our form, it is impossible to
disentangle the competing nucleation processes. We also find that the growth
rate and the shape of a crystal depends on when it nucleated. This is new
evidence that nucleation and growth are linked.Comment: 8 pages, plus 17 pages of supplementary materia
Cooperative motion and growing length scales in supercooled confined liquids
Using molecular dynamics simulations we investigate the relaxation dynamics
of a supercooled liquid close to a rough as well as close to a smooth wall. For
the former situation the relaxation times increase strongly with decreasing
distance from the wall whereas in the second case they strongly decrease. We
use this dependence to extract various dynamical length scales and show that
they grow with decreasing temperature. By calculating the frequency dependent
average susceptibility of such confined systems we show that the experimental
interpretation of such data is very difficult.Comment: 7 pages of Latex, 3 figure
Slow dynamics near glass transitions in thin polymer films
The -process (segmental motion) of thin polystyrene films supported
on glass substrate has been investigated in a wider frequency range from
10 Hz to 10 Hz using dielectric relaxation spectroscopy and thermal
expansion spectroscopy. The relaxation rate of the -process increases
with decreasing film thickness at a given temperature above the glass
transition. This increase in the relaxation rate with decreasing film thickness
is much more enhanced near the glass transition temperature. The glass
transition temperature determined as the temperature at which the relaxation
time of the -process becomes a macroscopic time scale shows a distinct
molecular weight dependence. It is also found that the Vogel temperature has
the thickness dependence, i.e., the Vogel temperature decreases with decreasing
film thickness. The expansion coefficient of the free volume is
extracted from the temperature dependence of the relaxation time within the
free volume theory. The fragility index is also evaluated as a function of
thickness. Both and are found to decrease with decreasing film
thickness.Comment: 9 pages, 7 figures, and 2 table
Dewetting of Glassy Polymer Films
Dynamics and morphology of hole growth in a film of power hardening
viscoplastic solid (yield stress ~ [strain-rate]^n) is investigated. At
short-times the growth is exponential and depends on the initial hole size. At
long-times, for n > 1/3, the growth is exponential with a different exponent.
However, for n < 1/3, the hole growth slows; the hole radius approaches an
asymptotic value as time tends to infinity. The rim shape is highly asymmetric,
the height of which has a power law dependence on the hole radius (exponent
close to unity for 0.25 < n < 0.4). The above results explain recent intriguing
experiments of Reiter, Phys. Rev. Lett, 87, 186101 (2001).Comment: 4 pages, 5 figures, RevTe
'You were quiet - I did all the marching': Research processes involved in hearing the voices of South Asian girls
This article is available open access through the publisher’s website at the link below. Copyright @ 2011
A B
Academic
Publishers.This article provides insights into the outcomes of reflection following two interview approaches used to explore narratives of the lived, individual experiences of South-Asian girls living in West London. In attempting to illuminate and re-present the cultural experiences as told by these girls, the choice of interview approach became critical in allowing the voices to be effectively heard (Rogers, 2005). This article therefore considers how a semi-structured interview approach offered valuable insights into the girls' experiences but became constraining for both researcher and participant in unveiling the complexity and depth of their lives. These constraints emerged through reflection by both participants and researcher. As a result of reflexivity during the research process, the researcher moved towards the use of research conversations during the second phase of the study. Ultimately the study revealed how the girls felt empowered by the opportunity to narrate their individual experiences and tell of their lives. In narrating their reflections on being part of the research, there was a clear recognition that the process facilitated the articulation of new voices and ‘multi-voicedness’ (Moen, 2006
In situ monitoring of latex film formation by small-angle neutron scattering: Evolving distributions of hydrophilic stabilizers in drying colloidal films
The distribution of hydrophilic species, such as surfactants, in latex films is of critical importance for the performance of adhesives, coatings and inks, among others. However, the evolution of this distribution during the film formation process and in the resulting dried films remains insufficiently elucidated. Here, we present in situ (wet) and ex situ (dry) SANS experiments that follow the film formation of two types of latex particles, which differ in their stabilizer: either a covalently bonded poly(methacrylic acid) (PMAA) segment or a physically adsorbed surfactant (sodium dodecyl sulfate, SDS). By fitting the experimental SANS data and combining with gravimetry experiments, we have ascertained the hydrophilic species distribution within the drying film and followed its evolution by correlating the size and shape of stabilizer clusters with the drying time. The evolution of the SDS distribution over drying time is being driven by a reduction in the interfacial free energy. However, the PMAA-based stabilizer macromolecules are restricted by their covalent bonding to core polymer chains and hence form high surface-area disc-like phases at the common boundary between particles and PMAA micelles. Contrary to an idealized view of film formation, the PMAA does not remain in the walls of a continuous honeycomb structure. The results presented here shed new light on the nanoscale distribution of hydrophilic species in drying and ageing latex films. We provide valuable insights into the influence of the stabilizer mobility on the final structure of latex films
The ‘sweet spot’ between submission and subversion: diaspora, education and the cosmopolitan project
A unique tRNA recognition mechanism of Caenorhabditis elegans mitochondrial EF-Tu2
Nematode mitochondria expresses two types of extremely truncated tRNAs that are specifically recognized by two distinct elongation factor Tu (EF-Tu) species named EF-Tu1 and EF-Tu2. This is unlike the canonical EF-Tu molecule that participates in the standard protein biosynthesis systems, which basically recognizes all elongator tRNAs. EF-Tu2 specifically recognizes Ser-tRNA(Ser) that lacks a D arm but has a short T arm. Our previous study led us to speculate the lack of the D arm may be essential for the tRNA recognition of EF-Tu2. However, here, we showed that the EF-Tu2 can bind to D arm-bearing Ser-tRNAs, in which the D–T arm interaction was weakened by the mutations. The ethylnitrosourea-modification interference assay showed that EF-Tu2 is unique, in that it interacts with the phosphate groups on the T stem on the side that is opposite to where canonical EF-Tu binds. The hydrolysis protection assay using several EF-Tu2 mutants then strongly suggests that seven C-terminal amino acid residues of EF-Tu2 are essential for its aminoacyl-tRNA-binding activity. Our results indicate that the formation of the nematode mitochondrial (mt) EF-Tu2/GTP/aminoacyl-tRNA ternary complex is probably supported by a unique interaction between the C-terminal extension of EF-Tu2 and the tRNA
Synthesis and characterization of polystyrene-blockpoly(vinylbenzoic acid): a promising compound for manipulating photoresponsive properties at the nanoscale
"Published online: 27 January 2015"Using reversible addition-fragmentation chain
transfer (RAFT) polymerization, the effect of PSt macroRAFT
and 4VBA ratio on the synthesis of a carboxylic
acid functional block copolymer (PSt-b-P4VBA) was
studied. PSt macroRAFT polymer was initially prepared
followed by the insertion of 4-vinylbenzoic acid (4VBA)
monomer. The chemical structure of the diblock copolymer
was confirmed by NMR and FTIR. The effect of PSt
macroRAFT and 4VBA ratio on copolymerization yield
and on molecular weight distribution was assessed by gel
permeation chromatography. The rate of polymerization
did not change as the 4VBA/PSt macroRAFT ratio
increased, indicating an ideal amount of 4VBA insertion.
An optimal ratio of [PSt macroRAFT]:[AIBN]:[4VBA]
was 1.2:1:180. DSC and XRD confirmed the amorphous
structure of homo and copolymer. Thermal stability was
higher for PSt-b-P4VBA forming activated porous carbon
char by dehydration, carbonization and oxidation. SEM
and STEM observations showed a morphological evolution
between PSt macroRAFT and the correspondent
copolymer.The authors acknowledge the n-STeP-Nanostructured systems for Tailored Performance, with reference NORTE-07-0124-FEDER-000039, supported by the Programa Operacional Regional do Norte (ON.2), PEst-C/CTM/LA0025/2013 (Strategic Project-LA 25-2013-2014)
Mechanochromic and thermochromic sensors based on graphene infused polymer opals
High quality opal‐like photonic crystals containing graphene are fabricated using evaporation‐driven self‐assembly of soft polymer colloids. A miniscule amount of pristine graphene within a colloidal crystal lattice results in the formation of colloidal crystals with a strong angle‐dependent structural color and a stop band that can be reversibly shifted across the visible spectrum. The crystals can be mechanically deformed or can reversibly change color as a function of their temperature, hence their sensitive mechanochromic and thermochromic response make them attractive candidates for a wide range of visual sensing applications. In particular, it is shown that the crystals are excellent candidates for visual strain sensors or integrated time‐temperature indicators which act over large temperature windows. Given the versatility of these crystals, this method represents a simple, inexpensive, and scalable approach to produce multifunctional graphene infused synthetic opals and opens up exciting applications for novel solution‐processable nanomaterial based photonics
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