Dehan Véronique, Bourgeat-Lami Elodie, D'Agosto Franck, Duffy Brendan, Fortini Andrea, Hilton Sharon, Krassa Kalliopi, Keddie Joseph, Koh Ming L., Lansalot Muriel, Lee Michelle, Lesage de la Haye Jennifer, Martin-Fabiani Ignacio, Mantzaridis Christos, Mazeffa Douglas P., Sear Richard, Schulz Malin, Sibbald Morgan, Skerry Brian, Thomas Brett (2017) High-performance water-based barrier coatings for the corrosion protection of structural steel, Steel Construction 10 (3) pp. 254-259
Ernst und Sohn
This article provides an overview of the outcomes of a European-funded project called BarrierPlus. A new type of water-based barrier coating was developed for structural steel applications. The advantages of this coating include enhanced moisture resistance, low volatile organic compounds (VOCs) and one-component self-crosslinking free of isocyanates. To enable this performance, a latex polymer binder was uniquely designed without using soap-like molecules, known as surfactants, to form the dispersion. By minimizing surfactants in the coating, the barrier properties were significantly enhanced. The latex was successfully scaled up to 15 kg quantities by an SME, coating formulations were scaled to pilot quantities and a variety of characterization and coating performance tests were completed. A life cycle assessment found that the BarrierPlus coating has a better environmental profile than an industry benchmark solvent-borne coating and showed promising results relative to commercial waterborne benchmarks.
Sear RP (2002) Distribution of the second virial coefficients of globular proteins, Europhysics Letters 60 pp. 938-944
George and Wilson [Acta. Cryst. D 50, 361 (1994)] looked at the distribution
of values of the second virial coefficient of globular proteins, under the
conditions at which they crystallise. They found the values to lie within a
fairly narrow range. We have defined a simple model of a generic globular
protein. We then generate a set of proteins by picking values for the
parameters of the model from a probability distribution. At fixed solubility,
this set of proteins is found to have values of the second virial coefficient
that fall within a fairly narrow range. The shape of the probability
distribution of the second virial coefficient is Gaussian because the second
virial coefficient is a sum of contributions from different patches on the
Mithen JP, Callison AJ, Sear RP (2015) Nucleation of crystals that are mixed composites of all three polymorphs in the Gaussian core model., The Journal of chemical physics 142 (22)
We present results of computer simulations of homogeneous crystal nucleation in the Gaussian core model. In our simulations, we study the competition between the body-centered-cubic (bcc), face-centered-cubic (fcc), and hexagonal-close-packed crystal phases. We find that the crystal nuclei that form from the metastable fluid phase are typically "mixed"; they do not consist of a single crystal polymorph. Furthermore, when the fcc phase is stable or fcc and bcc phases are equally stable, this mixed nature is found to persist far beyond the size at the top of the nucleation barrier, that is, far into what would be considered the growth (rather than nucleation) regime. In this region, the polymorph that forms is therefore selected long after nucleation. This has implications. When nucleation is slow, it will be the rate-limiting step for crystallization. Then, the step that determines the time scale for crystallisation is different from the step that controls which polymorph forms. This means that they can be independently controlled. Also between nucleation and polymorph selection, there is a growing phase that is clearly crystalline not fluid, but this phase cannot be assigned to any one polymorph.
Tavassoli Z, Sear RP (2001) Homogeneous nucleation near a second phase transition and Ostwald's step
rule, J. Chemical Physics 116 pp. 5066-5072
Homogeneous nucleation of the new phase of one transition near a second phase
transition is considered. The system has two phase transitions, we study the
nucleation of the new phase of one of these transitions under conditions such
that we are near or at the second phase transition. The second transition is an
Ising-like transition and lies within the coexistence region of the first
transition. It effects the formation of the new phase in two ways. The first is
by reducing the nucleation barrier to direct nucleation. The second is by the
system undergoing the second transition and transforming to a state in which
the barrier to nucleation is greatly reduced. The second way occurs when the
barrier to undergoing the second phase transition is less than that of the
first phase transition, and is in accordance with Ostwald's rule.
Sear RP (2004) A model for the accidental catalysis of protein unfolding in vivo, EPL (Europhysics Letters)
Activated processes such as protein unfolding are highly sensitive to
heterogeneity in the environment. We study a highly simplified model of a
protein in a random heterogeneous environment, a model of the in vivo
environment. It is found that if the heterogeneity is sufficiently large the
total rate of the process is essentially a random variable; this may be the
cause of the species-to-species variability in the rate of prion protein
conversion found by Deleault et al. [Nature, 425 (2003) 717].
It is well known amongst molecular biologists that proteins with a common
ancestor and that perform the same function in similar organisms, can have
rather different amino-acid sequences. Mutations have altered the amino-acid
sequences without affecting the function; this is called neutral evolution. A
simple model of a protein in which the interactions are encoded by sequences of
bits is introduced, and used to study how mutations can change these bits, and
hence the interactions, while maintaining the stability of the protein
solution. This stability is a simple minimal requirement on our model proteins
which mimics part of the requirement on a real protein to be functional. The
properties of our model protein, such as its second virial coefficient, are
found to vary significantly from one model protein to another. It is suggested
that this may also be the case for real proteins in vivo.
If many micelles adsorb onto the same polymer molecule then they are said to
form a necklace. A minimal model of such a necklace is proposed and shown to be
almost equivalent to a 1-dimensional fluid with nearest-neighbour interactions.
The thermodynamic functions of this fluid are obtained and then used to predict
the change in the critical micellar concentration of the surfactant in the
presence of the polymer. If the amount of polymer is not too large there are
two critical micellar concentrations, one for micelles in necklaces and one for
Proteins must bind to specific other proteins in vivo in order to function.
The proteins must bind only to one or a few other proteins of the of order a
thousand proteins typically present in vivo. Using a simple model of a protein,
specific binding in many component mixtures is studied. It is found to be a
demanding function in the sense that it demands that the binding sites of the
proteins be encoded by long sequences of bits, and the requirement for specific
binding then strongly constrains these sequences. This is quantified by the
capacity of proteins of a given size (sequence length), which is the maximum
number of specific-binding interactions possible in a mixture. This calculation
of the maximum number possible is in the same spirit as the work of Shannon and
others on the maximum rate of communication through noisy channels.
Sear RP (2002) Interfacial tension and nucleation in mixtures of colloids and long
ideal polymer coils, Physical Review E 65
Mixtures of ideal polymers with hard spheres whose diameters are smaller than
the radius of gyration of the polymer, exhibit extensive immiscibility. The
interfacial tension between demixed phases of these mixtures is estimated, as
is the barrier to nucleation. The barrier is found to scale linearly with the
radius of the polymer, causing it to become large for large polymers. Thus for
large polymers nucleation is suppressed and phase separation proceeds via
spinodal decomposition, as it does in polymer blends.
Sear RP (1997) A coil-globule transition of a semiflexible polymer driven by the
addition of spherical particles, Phys.Rev. E 58 pp. 724-728
The phase behaviour of a single large semiflexible polymer immersed in a
suspension of spherical particles is studied. All interactions are simple
excluded volume interactions and the diameter of the spherical particles is an
order of magnitude larger than the diameter of the polymer. The spherical
particles induce a quite long ranged depletion attraction between the segments
of the polymer and this induces a continuous coil-globule transition in the
polymer. This behaviour gives an indication of the condensing effect of
macromolecular crowding on DNA.
Sear RP (2000) Nucleation of a non-critical phase in a fluid near a critical point, Journal of Chemical Physics v 114 pp. 3170-3173
Phase diagrams of some globular proteins have a fluid-fluid transition as
well as a fluid-crystal transition. Homogeneous nucleation of the crystal from
the fluid phase near the critical point of the fluid-fluid transition is
examined. As the fluid-fluid critical point is approached, the number of
molecules in the critical nucleus, the nucleus at the top of the free energy
barrier to nucleation, is found to diverge as the isothermal compressibility.
This divergence is due to a layer of the fluid phase of width equal to the
fluid's correlation length which surrounds the core of the nucleus; the number
of molecules in a crystalline environment in the nucleus does not diverge. The
free energy barrier to nucleation remains finite but its derivative with
respect to the chemical potential is equal to minus the number of molecules in
the critical nucleus and so diverges.
Crystals form via nucleation followed by growth. Often nucleation data are interpreted using the classical theory of nucleation, which is essentially a simple theory for the nucleation of a fluid phase. I characterise this classical theory as making six assumptions; I discuss each assumption in turn. I then review experiments and simulations that find nucleation behaviour that cannot be described by the classical theory. The experiments are on the crystallisation from solution of molecules such as drugs and related molecules, ice and calcium carbonate. The review also covers work on non-classical nucleation in solutions of the protein lysozyme, and work on the fascinating phenomenon of nucleation induced by laser pulses. I hope this review will be of interest to those studying the crystallisation of both molecules and ions from solution. The review aims to advance our understanding of the crucial first step in crystallisation, and to enable researchers studying crystallisation in one system to learn from what others have done in studying analogous phenomena in different systems. © 2012 Institute of Materials, Minerals and Mining and ASM International.
Sear RP (2005) Formation of a metastable phase due to the presence of impurities, J. Phys.: Condens. Matter 17 pp. 3997-4004
Phase transitions into a new phase that is itself metastable are common;
instead of the equilibrium phase nucleating a metastable phase does so. When
this occurs the system is sometimes said to be obeying Ostwald's rule. We show
how this can happen when there are impurities present that reduce the barrier
to heterogeneous nucleation of the metastable phase. We do so by studying a
Potts lattice model using Monte Carlo simulation. Thus, which phase forms
depends not only on the properties of the different phases but also on the
impurities present. Understanding why systems obey Ostwald's rule may therefore
require a study of the impurities present.
van Meel JA, Page AJ, Sear RP, Frenkel D (2008) Two-step vapor-crystal nucleation close below triple point, JOURNAL OF CHEMICAL PHYSICS 129 (20) ARTN 204505 AMER INST PHYSICS
Asanithi P, Saridakis E, Govada L, Jurewicz I, Brunner EW, Ponnusamy R, Cleaver JAS, Dalton AB, Chayen NE, Sear RP (2009) Carbon-nanotube-based materials for protein crystallization, ACS Applied Materials and Interfaces 1 (6) pp. 1203-1210
We report on the first use of carbon-nanotube-based films to produce crystals of proteins. The crystals nucleate on the surface of the film. The difficulty of crystallizing proteins is a major bottleneck in the determination of the structure and function of biological molecules. The crystallization of two model proteins and two medically relevant proteins was studied. Quantitative data on the crystallization times of the model protein lysozyme are also presented. Two types of nanotube films, one made with the surfactant Triton X-100 (TX-100) and one with gelatin, were tested. Both induce nucleation of the crystal phase at supersaturations at which the protein solution would otherwise remain clear; however, the gelatin-based film induced nucleation down to much lower supersaturations for the two model proteins with which it was used. It appears that the interactions of gelatin with the protein molecules are particularly favorable to nucleation. Crystals of the C1 domain of the human cardiac myosin-binding protein-C that diffracted to a resolution of 1.6 Å were obtained on the TX-100 film. This is far superior to the best crystals obtained using standard techniques, which only diffracted to 3.0 Å. Thus, both of our nanotube-based films are very promising candidates for future work on crystallizing difficult-to-crystallize target proteins. © 2009 American Chemical Society.
Bajanca F, Gonzalez-Perez V, Gillespie SJ, Beley C, Garcia L, Theveneau E, Sear RP, Hughes SM (2015) In vivo dynamics of skeletal muscle Dystrophin in zebrafish embryos revealed by improved FRAP analysis, ELIFE 4 ARTN e06541 ELIFE SCIENCES PUBLICATIONS LTD
Sear RP (1997) Scattering from small colloidal particles in a semidilute polymer
solution, European Physical Journal B v 1 pp. 313-317
The correlations between the segments of a semidilute polymer solution are
found to induce correlations in the positions of small particles added to the
solution. Small means a diameter much less than the polymer's correlation
length. In the presence of polymer the particles behave as if they attracted
each other. It is shown how the polymer's correlation length may be determined
from a scattering experiment performed on the spheres.
We consider the nucleation of a crystal phase, on a crystalline surface of a different substance. Sixty years ago, Turnbull and Vonnegut predicted that a crystalline surface is best at inducing nucleation of another crystal when there is a perfect epitaxial match between the two bulk lattices. We use computer simulation to show that this is not quite right. In fact, the crystal lattice of a finite nucleus is strained from that in the bulk, and nucleation is fastest when the surface matches this strained lattice. We also find that the approach of Hillier and Ward predicts when nucleation is epitaxial. © Copyright EPLA, 2014.
Sear RP (2001) Nucleation of the crystalline phase of proteins in the presence of
semidilute non-adsorbing polymer, Journal of Chemical Physics
Starting from a protein solution which is metastable with respect to the
crystalline phase, the effect of adding semidilute non-adsorbing polymer is
considered. It is found to increase the chemical potential of the protein by a
few tenths of kT, which may be enough to lower the barrier to nucleation of the
crystalline phase by enough to allow crystallisation. It is also shown that
assuming that the polymer induces a pairwise additive attraction leads to
qualitatively incorrect results.
Jurewicz I, King AAK, Worajittiphon P, Asanithi P, Brunner EW, Sear RP, Hosea TJC, Keddie JL, Dalton AB (2010) Colloid-Assisted Self-Assembly of Robust, Three-Dimensional Networks of Carbon Nanotubes over Large Areas, MACROMOLECULAR RAPID COMMUNICATIONS 31 (7) pp. 609-615 WILEY-V C H VERLAG GMBH
Sear RP (2002) Flory-Huggins theory for athermal mixtures of hard spheres and larger
flexible polymers, Physical Review E 66
A simple analytic theory for mixtures of hard spheres and larger polymers
with excluded volume interactions is developed. The mixture is shown to exhibit
extensive immiscibility. For large polymers with strong excluded volume
interactions, the density of monomers at the critical point for demixing
decreases as one over the square root of the length of the polymer, while the
density of spheres tends to a constant. This is very different to the behaviour
of mixtures of hard spheres and ideal polymers, these mixtures although even
less miscible than those with polymers with excluded volume interactions, have
a much higher polymer density at the critical point of demixing. The theory
applies to the complete range of mixtures of spheres with flexible polymers,
from those with strong excluded volume interactions to ideal polymers.
Brunner EW, Jurewicz I, Heister E, Fahimi A, Bo C, Sear RP, Dalton AB, Donovan PJ (2014) Growth and proliferation of human embryonic stem cells on fully synthetic scaffolds based on carbon nanotubes, ACS Applied Materials and Interfaces 6 (4) pp. 2598-2603
Here we show an industrially scalable and inexpensive method of fabricating entirely synthetic, non-xenogeneic carbon nanotube-based scaffolds by vacuum filtration for the culture of human embryonic stem cells. We show that controlled exposure of carbon nanotubes to sonication and the amount of energy delivered to the dispersion directly impacts the surface properties, allowing for control over the nanotopography of the resulting carbon nanotube films, which in turn has demonstrable effects upon in vitro human embryonic stem cells cultures. By altering the nanotube processing conditions before film fabrication, it is possible to influence cell adherence, proliferation and colony morphology. Such a tunable surface with capabilities of influencing stem cell behaviors, combined with the ability to slow or speed population doubling times, will provide crucial solutions for achieving applications envisioned by stem cell biologists to assist future industrial and clinical implementation of human embryonic stem cells. © 2014 American Chemical Society.
Sear RP (2005) The cytoplasm of living cells: a functional mixture of thousands of components, JOURNAL OF PHYSICS-CONDENSED MATTER 17 (45) pp. S3587-S3595 IOP PUBLISHING LTD
Sear RP (1998) The stability limit of polydisperse sticky hard spheres,
It has been shown by Stell [J. Stat. Phys. 63, 1203 (1991)] that at low
temperature monodisperse sticky spheres collapse to form coexisting
close-packed solid and infinitely dilute gases. We show that polydisperse
sticky spheres also collapse and calculate the collapse temperature. The
polydisperse spheres separate into fractions with narrower polydispersities
which can then solidify. This is the first example of a single-peaked
polydisperse mixture phase separating. It implies that a mixture of
polydisperse large hard spheres with much smaller hard spheres does not show
Sear RP, Pagonabarraga I, Flaus A (2015) Life at the mesoscale: The self-organised cytoplasm and nucleoplasm, BMC Biophysics 8 (1)
© 2015 Sear et al.The cell contains highly dynamic structures exploiting physical principles of self-organisation at the mesoscale (100 nm to 10 ¼m). Examples include non-membrane bound cytoplasmic bodies, cytoskeleton-based motor networks and multi-scale chromatin organisation. The challenges of mesoscale self-organisation were discussed at a CECAM workshop in July 2014. Biologists need approaches to observe highly dynamic, low affinity, low specificity associations and to perturb single structures, while biological physicists and biomathematicians need to work closely with biologists to build and validate quantitative models. A table of terminology is included to facilitate multidisciplinary efforts to reveal the richness and diversity of mesoscale cell biology.
Keddie JL, Andrei DC, Sear RPL, Yeates SG (1999) Surface flattening of thermosetting powder coatings: Theory and experiment., ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 218 pp. U626-U626 AMER CHEMICAL SOC
Sear RP (2006) On the interpretation of quantitative experimental data on nucleation rates using classical nucleation theory, JOURNAL OF PHYSICAL CHEMISTRY B 110 (43) pp. 21944-21949 AMER CHEMICAL SOC
Sear RP (2014) Quantitative studies of crystal nucleation at constant supersaturation: Experimental data and models, CrystEngComm 16 (29) pp. 6506-6522
Crystallisation starts off with nucleation, which is rather poorly understood. However, over the last few years there have been important quantitative experiments at constant supersaturation, and the modelling of this data has also advanced. Experiments in which the supersaturation is varying, e.g., those at constant cooling rate, are important but hard to interpret. This review focuses on the state of the art in quantitative studies of nucleation at constant supersaturation. We can now test reliably for heterogeneous nucleation and somewhat less reliably for the rarer case of homogeneous nucleation. In the case of heterogeneous nucleation, we can also obtain at least some information on what is responsible for nucleation. We also now have (unfortunately currently untested) predictions for the scaling of nucleation timescales with system size. These predictions may prove important both for scaling up from small droplets to larger volumes, and for scaling down to crystallisation at the nanoscales relevant for nanotechnology applications. Finally, it is worth noting that in many experiments the dynamic range of nucleation times is too large to be measured. This is presumably due to highly variable impurities, and this problem may need to be addressed in future work. This journal is © the Partner Organisations 2014.
Using computer simulations, we study a nonequilibrium state with a liquid-like S(k) but where over 95% of the molecules are in locally crystalline environments. Due to its liquid-like S(k) and slow dynamics, the state is apparently amorphous, although it contains nanocrystalline order. This nanocrystalline order can strongly bias the polymorph that forms when the state crystallizes.
First order phase transitions proceed via nucleation. The rate of nucleation
varies exponentially with the free-energy barrier to nucleation, and so is
highly sensitive to variations in this barrier. In practice, very few systems
are absolutely pure, there are typically some impurities present which are
rather poorly characterised. These interact with the nucleus, causing the
barrier to vary, and so must be taken into account. Here the impurity-nucleus
interactions are modelled by random variables. The rate then has the same form
as the partition function of Derrida's Random Energy Model, and as in this
model there is a regime in which the behaviour is non-self-averaging.
Non-self-averaging nucleation is nucleation with a rate that varies
significantly from one realisation of the random variables to another. In
experiment this corresponds to variation in the nucleation rate from one sample
to another. General analytic expressions are obtained for the crossover from a
self-averaging to a non-self-averaging rate of nucleation.
Sear RP (2015) Liquids that form due to dynamics of the molecules that depend on the
RNA molecules in living cells form what look like liquid droplets formed by
liquid/liquid phase separation. But unlike the molecules in conventional phase
separating mixtures, RNA molecules are transported by molecular motors that
consume energy and so are out of equilibrium. Motivated by this we consider
what sort of simple rules for the dynamics of model mRNA molecules lead to
liquid/liquid phase separation. We find that dynamics that slow as the local
density of molecules increases, drive the formation of liquids. We also look at
the analogous separation of the two blocks of a block copolymer, in which the
monomers of one block have dynamics that depend on the local density of
monomers of that block. We find that this block condenses and separates from
the monomers of the other block. This is a simple model of the
out-of-equilibrium domain formation found in the chromatin in the nucleus of
Keddie JL, Ekanayake P, Koenig AM, Weerakkody TG, Barber N, Johannsmann D, Sear RP, McDonald PJ (2007) Influence of the colloidal stability of latex particles on their distribution in drying films, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY 234 AMER CHEMICAL SOC
Homogeneous nucleation of a new phase near an Ising-like critical point of
another phase transition is studied. A scaling analysis shows that the free
energy barrier to nucleation contains a singular term with the same scaling as
the order parameter associated with the critical point. The total magnetisation
of the nucleus scales as the response function and so it diverges.
Vapour-liquid critical points are in the Ising universality class and so our
results imply that near such a critical point the number of molecules in a
nucleus of a another phase, such as a crystalline phase, diverges as the
isothermal compressibility. The case where symmetry prevents coupling between
the nucleus and the order parameter is also considered.
Sear RP (1999) Fluid-fluid transitions of hard spheres with a very short-range
attraction, Physical Review E v 61 pp. 6019-6022
Hard spheres with an attraction of range a tenth to a hundredth of the sphere
diameter are constrained to remain fluid even at densities when monodisperse
particles at equilibrium would have crystallised, in order to compare with
experimental systems which remain fluid. They are found to have a fluid-fluid
transition at high density. As the range of the attraction tends to zero, the
density at the critical point tends towards the random-close-packing density of
Sear RP (2000) Molecular dynamics of a dense fluid of polydisperse hard spheres, Journal of Chemical Physics v 113 pp. 4732-4739
Slow dynamics in a fluid are studied in one of the most basic systems
possible: polydisperse hard spheres. Monodisperse hard spheres cannot be
studied as the slow down in dynamics as the density is increased is preempted
by crystallisation. As the dynamics slow they become more heterogeneous, the
spread in the distances traveled by different particles in the same time
increases. However, the dynamics appears to be less heterogeneous than in
hard-sphere-like colloids at the same volume fraction. The particles which move
least far in a characteristic relaxation time and, particularly, the particles
which move farthest in the same time are clustered, not randomly distributed
throughout the sample. We study the dynamics at three different widths of the
distribution of diameters of the hard spheres. For each width, the relaxation
time is the same function of the compressibility factor, suggesting that this
determines the relaxation time for hard spheres.
Biominerals are typically composites of hard matter such as calcite, and soft matter such as proteins. There is currently considerable interest in how the soft matter component is incorporated into the hard matter component. This would typically be a protein that does not fold up into a single rigid domain but is closer to a simple polymer, being incorporated into a growing inorganic crystal in aqueous solution. Here I use computer simulation to study a very simple (2D lattice gas) model of a growing phase and a polymer. This allows me to study the microscopic dynamics of incorporation or rejection of a single polymer by the growing phase. It also allows me to look at how high concentrations of absorbing polymer can both arrest crystal growth, and change the shape of crystals. I find that the incorporation of a single polymer into the growing phase is due to slow dynamics of the polymer at the growth front. These slow dynamics are then unable to keep up with the advancing growth front. This is an intrinsically far-from-equilibrium process and so occurs even when incorporation is thermodynamically highly unfavourable. During the incorporation process, large polymers create large and deep, but transient, pits in the growth front. © The Royal Society of Chemistry 2012.
Bacteria typically have a few thousand different proteins. The number of
proteins with a given charge is a roughly Gaussian function of charge - centred
near zero, and with a width around ten (in units of the charge on the proton).
We have used the charges on E. coli's proteins to estimate the changes in the
second virial coefficients of all its proteins as the concentration of a 1:1
salt is increased. The second virial coefficient has dimensions of volume and
we find that on average it decreases by about twice the average volume of a
protein when the salt concentration is increased from 0.2 to 1 Molar. The
standard deviation of the decrease is of the same order. The consequences of
this for the complex mixture of proteins inside an E. coli cell, are briefly
Brunner EW, Jurewicz I, Heister E, Fahimi A, Bo C, Sear RP, Donovan PJ, Dalton AB (2014) Growth and proliferation of human embryonic stem cells on fully synthetic scaffolds based on carbon nanotubes., ACS Appl Mater Interfaces 6 (4) pp. 2598-2603
Here we show an industrially scalable and inexpensive method of fabricating entirely synthetic, non-xenogeneic carbon nanotube-based scaffolds by vacuum filtration for the culture of human embryonic stem cells. We show that controlled exposure of carbon nanotubes to sonication and the amount of energy delivered to the dispersion directly impacts the surface properties, allowing for control over the nanotopography of the resulting carbon nanotube films, which in turn has demonstrable effects upon in vitro human embryonic stem cells cultures. By altering the nanotube processing conditions before film fabrication, it is possible to influence cell adherence, proliferation and colony morphology. Such a tunable surface with capabilities of influencing stem cell behaviors, combined with the ability to slow or speed population doubling times, will provide crucial solutions for achieving applications envisioned by stem cell biologists to assist future industrial and clinical implementation of human embryonic stem cells.
Sear RP (2003) Protein crystals and charged surfaces: interactions and heterogeneous
nucleation, Physical Review E 67
As proteins typically have charges of around 10, they will interact strongly
with charged surfaces. We calculate the electrostatic contribution to the
interaction of crystals of protein with charged surfaces. The surfaces repel
like-charged crystals and attract oppositely-charged crystals, with free
energies which can be easily several kT per protein molecule brought into
contact with the surface. This means that oppositely charged surfaces can act
as a nucleant, they can induce nucleation of a protein crystal by lowering the
free energy barrier to heterogeneous nucleation of the crystal from a dilute
We present results of computer simulations of crystal nucleation on a crystalline surface, in the Lennard-Jones model. Motivated by the pioneering work of Turnbull and Vonnegut [Ind. Eng. Chem. 44, 1292 (1952)], we investigate the effects of a mismatch between the surface lattice constant and that of the bulk nucleating crystal. We find that the nucleation rate is maximum close to, but not exactly at, zero mismatch. The offset is due to the finite size of the nucleus. In agreement with a number of experiments, we find that even for large mismatches of 10% or more, the formation of the crystal can be epitaxial, meaning that the crystals that nucleate have a fixed orientation with respect to the surface lattice. However, nucleation is not always epitaxial, and loss of epitaxy does affect how the rate varies with mismatch. The surface lattice strongly influences the nucleation rate. We show that the epitaxy observed in our simulations can be predicted using calculations of the potential energy between the surface and the first layer of the nucleating crystal, in the spirit of simple approaches such as that of Hillier and Ward [Phys. Rev. B 54, 14037 (1996)].
Chayen NE, Saridakis E, Sear RP (2006) Experiment and theory for heterogeneous nucleation of protein crystals in a porous medium, PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA 103 (3) pp. 597-601 NATL ACAD SCIENCES
Homogeneous nucleation of a new phase near a second, continuous, transition,
is considered. The continuous transition is in the metastable region associated
with the first-order phase transition, one of whose coexisting phases is
nucleating. Mean-field calculations show that as the continuous transition is
approached, the size of the nucleus varies as the response function of the
order parameter of the continuous transition. This response function diverges
at the continuous transition, as does the temperature derivative of the free
energy barrier to nucleation. This rapid drop of the barrier as the continuous
transition is approached means that the continuous transition acts to reduce
the barrier to nucleation at the first-order transition. This may be useful in
the crystallisation of globular proteins.
Sear RP, Cuesta JA (2003) Instabilities in complex mixtures with a large number of components, Phys. Rev. Lett. 91
Inside living cells are complex mixtures of thousands of components. It is
hopeless to try to characterise all the individual interactions in these
mixtures. Thus, we develop a statistical approach to approximating them, and
examine the conditions under which the mixtures phase separate. The approach
approximates the matrix of second virial coefficients of the mixture by a
random matrix, and determines the stability of the mixture from the spectrum of
such random matrices.
Meldrum FC, Sear RP (2008) MATERIALS SCIENCE Now You See Them, SCIENCE 322 (5909) pp. 1802-1803 AMER ASSOC ADVANCEMENT SCIENCE
At low temperature, spheres with a very short-ranged attraction exist as a
close-packed solid coexisting with an infinitely dilute gas. We find that the
ratio of the interfacial tension between these two phases to the thermal energy
diverges as the range of the attraction goes to zero. The large tensions when
the interparticle attractions are short-ranged may be why globular proteins
only crystallise over a narrow range of conditions.
Sear RP (1997) The coil-globule transition of polymers of long rigid monomers connected
by flexible spacers, Journal of Chemical Physics
A simple model of a polymer with long rigid segments which interact via
excluded volume repulsions and short ranged attractions is proposed. The
coil-globule transition of this model polymer is strongly first order, the
globule is crystalline and the coil which coexists with the globule is swollen.
A virial expansion truncated at low order is shown to provide a very poor
approximation to the free energy and so a cell theory is used to calculate the
free energy of the globule.
Sear RP, Warren PB (2002) On the electrical double layer contribution to the interfacial tension
of protein crystals, Journal of Chemical Physics
We study the electrical double layer at the interface between a protein
crystal and a salt solution or a dilute solution of protein, and estimate the
double layer's contribution to the interfacial tension of this interface. This
contribution is negative and decreases in magnitude with increasing salt
concentration. We also consider briefly the interaction between a pair of
Sear RP (2011) Crystal nucleation: In a tight corner., Nat Mater 10 (11) pp. 809-810
Sear RP (2006) Interactions in protein solutions, CURRENT OPINION IN COLLOID & INTERFACE SCIENCE 11 (1) pp. 35-39 ELSEVIER SCIENCE LONDON
Khatri BS, McLeish TCB, Sear RP (2009) Statistical mechanics of convergent evolution in spatial patterning, PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA 106 (24) pp. 9564-9569 NATL ACAD SCIENCES
Abdullah CA, Asanithi P, Brunner EW, Jurewicz I, Bo C, Azad CL, Ovalle-Robles R, Fang S, Lima MD, Lepro X, Collins S, Baughman RH, Sear RP, Dalton AB (2011) Aligned, isotropic and patterned carbon nanotube substrates that control the growth and alignment of Chinese hamster ovary cells., Nanotechnology 22 (20)
Institute of Physics
Here we culture Chinese hamster ovary cells on isotropic, aligned and patterned substrates based on multiwall carbon nanotubes. The nanotubes provide the substrate with nanoscale topography. The cells adhere to and grow on all substrates, and on the aligned substrate, the cells align strongly with the axis of the bundles of the multiwall nanotubes. This control over cell alignment is required for tissue engineering; almost all tissues consist of oriented cells. The aligned substrates are made using straightforward physical chemistry techniques from forests of multiwall nanotubes; no lithography is required to make inexpensive large-scale substrates with highly aligned nanoscale grooves. Interestingly, although the cells strongly align with the nanoscale grooves, only a few also elongate along this axis: alignment of the cells does not require a pronounced change in morphology of the cell. We also pattern the nanotube bundles over length scales comparable to the cell size and show that the cells follow this pattern.
Sear RP (1999) Phase behaviour of a simple model of globular proteins, Journal of Chemical Physics v 111 pp. 4800-4806
A simple model of globular proteins which incorporates anisotropic
attractions is proposed. It is closely related to models used to model simple
hydrogen-bonding molecules such as water. Theories for both the fluid and solid
phases are presented, and phase diagrams calculated. The model protein exhibits
a fluid-fluid transition which is metastable with respect to the fluid-solid
transition for most values of the model parameters. This is behaviour often
observed for globular proteins. The model offers an explanation of the
difficulty observed in crystallising some globular proteins and suggests that
some proteins may not have a solid phase at all under all but extreme
Sear RP (2000) Phase separation in mixtures of colloids and long ideal polymer coils, Physical Review Letters v 86 pp. 4696-4699
Colloidal suspensions with free polymer coils which are larger than the
colloidal particles are considered. The polymer-colloid interaction is modeled
by an extension of the Asakura-Oosawa model. Phase separation occurs into
dilute and dense fluid phases of colloidal particles when polymer is added. The
critical density of this transition tends to zero as the size of the polymer
Che Abdullah CA, Azad CL, Ovalle-Robles R, Fang S, Lima MD, Lepró X, Collins S, Baughman RH, Dalton AB, Plant NJ, Sear RP (2014) Primary liver cells cultured on carbon nanotube substrates for liver tissue engineering and drug discovery applications., ACS Appl Mater Interfaces 6 (13) pp. 10373-10380
Here, we explore the use of two- and three-dimensional scaffolds of multiwalled-carbon nanotubes (MWNTs) for hepatocyte cell culture. Our objective is to study the use of these scaffolds in liver tissue engineering and drug discovery. In our experiments, primary rat hepatocytes, the parenchymal (main functional) cell type in the liver, were cultured on aligned nanogrooved MWNT sheets, MWNT yarns, or standard 2-dimensional culture conditions as a control. We find comparable cell viability between all three culture conditions but enhanced production of the hepatocyte-specific marker albumin for cells cultured on MWNTs. The basal activity of two clinically relevant cytochrome P450 enzymes, CYP1A2 and CYP3A4, are similar on all substrates, but we find enhanced induction of CYP1A2 for cells on the MWNT sheets. Our data thus supports the use of these substrates for applications including tissue engineering and enhancing liver-specific functions, as well as in in vitro model systems with enhanced predictive capability in drug discovery and development.
Sear RP (2007) Dishevelled: a protein that functions in living cells by phase separating, SOFT MATTER 3 (6) pp. 680-684 ROYAL SOC CHEMISTRY
Sear RP (1999) Absence of the liquid phase when the attraction is not pairwise additive, Physical Review E 61 pp. 651-655
Recent work on charged colloidal suspensions with very low levels of added
salt has suggested that although pairs of the colloidal particles repel,
clusters of the particles attract. Motivated by this, we study simple model
particles which have many-body attractions. These attractions are generic
many-body attractions and are not calculated for any specific colloidal
suspension. We find that many-body attractions can stabilise solid phases at
low pressures but that the liquid phase is either completely absent from the
equilibrium phase diagram or present only within a small region of parameter
Sear RP (1997) Polymer induced phase coexistence in systems of lamellar phases,
The effect of adding nonadsorbing polymer to a lamellar phase of surfactant
bilayers is studied theoretically. We find that the polymer produces
coexistence between two lamellar phases of different layer spacings. The
coexistence region is a closed loop, as in the experiments of Ficheux et al.
[J. de Physique II 5 823 (1995)]. Within our model the coexistence is driven by
Sear RP (1999) Classical nucleation theory for the nucleation of the solid phase of
spherical particles with a short-ranged attraction, Journal of Chemical Physics v 111 pp. 2001-2007
Classical nucleation theory is used to estimate the free-energy barrier to
nucleation of the solid phase of particles interacting via a potential which
has a short-ranged attraction. Due to the high interfacial tension between the
fluid and solid phases, this barrier is very large, much larger than in hard
spheres. It is divergent in the limit that the range of the attraction tends to
zero. We predict an upper limit on nucleation in good agreement with the
results of experiments on the crystallisation of proteins.
Sear RP (2008) Phase separation of equilibrium polymers of proteins in living cells, FARADAY DISCUSSIONS 139 pp. 21-34 ROYAL SOC CHEMISTRY
Sear RP (2008) Nucleation of a liquid on aerosol nanoparticles, EPL-EUROPHYS LETT 83 (6) 66002 pp. 1-6 EDP SCIENCES
Nucleation of liquid water in the Earth?s atmosphere occurs via heterogeneous
nucleation on aerosol particles. We consider nucleation on both water-insoluble and water-soluble
aerosol particles. We find that, for particles of the same radius, nucleation on soluble particles
dominates. Soluble particles dissolve in the liquid phase and form a droplet even at coexistence.
The radius of this droplet essentially determines the supersaturation at which nucleation occurs:
the larger the droplet the smaller the supersaturation required before it nucleates to form the bulk
liquid. We find that the supersaturation is best measured by the Kelvin radius, which is the radius
of a droplet of pure liquid that coexists with vapour of a given supersaturation. We show that
nucleation occurs at a universal value of the ratio between the radius of the droplet at coexistence
and the Kelvin radius.
Sear RP (2002) Heterogeneous nucleation near a metastable vapour-liquid transition: the
effect of wetting transitions, J. Physics: Condensed Matter 14 pp. 3693-3703
Phase transformations such as freezing typically start with heterogeneous
nucleation. Heterogeneous nucleation near a wetting transition, of a
crystalline phase is studied. The wetting transition occurs at or near a
vapour-liquid transition which occurs in a metastable fluid. The fluid is
metastable with respect to crystallisation, and it is the crystallisation of
this fluid phase that we are interested in. At a wetting transition a thick
layer of a liquid phase forms at a surface in contact with the vapour phase.
The crystalline nucleus is then immersed in this liquid layer, which reduces
the free energy barrier to nucleation and so dramatically increases the
nucleation rate. The variation in the rate of heterogeneous nucleation close to
wetting transitions is calculated for systems in which the longest-range forces
are dispersion forces.
Colloidal particles are not simple rigid particles, in general an isolated
particle is a system with many degrees of freedom in its own right, e.g., the
counterions around a charged colloidal particle.The behaviour of model
colloidal particles, with a simple phenomenological model to account for these
degrees of freedom, is studied. It is found that the interaction between the
particles is not pairwise additive. It is even possible that the interaction
between a triplet of particles is attractive while the pair interaction is
repulsive. When this is so the liquid phase is either stable only in a small
region of the phase diagram or absent altogether.
Sear RP (1999) Metastability and nucleation in the dilute fluid phase of a simple model
of globular proteins,
The dilute fluid phase of model globular proteins is studied. The model
possesses a fluid-fluid transition buried within the fluid-crystal coexistence
region, as do some globular proteins. If this fluid-fluid transition is not
buried deep inside the fluid-crystal coexistence region the crystalline phase
does not nucleate within the dilute fluid. We link this lack of nucleation of
the crystal to the interactions in our model and speculate that similar
interactions between globular proteins are responsible for the difficulty found
in crystallising many globular proteins.
Sear RP, Cuesta JA (2000) What do emulsification failure and Bose-Einstein condensation have in
common?, Europhys. Lett. 55
Ideal bosons and classical ring polymers formed via self-assembly, are known
to have the same partition function, and so analogous phase transitions. In
ring polymers, the analogue of Bose-Einstein condensation occurs when a ring
polymer of macroscopic size appears. We show that a transition of the same
general form occurs within a whole class of systems with self-assembly, and
illustrate it with the emulsification failure of a microemulsion phase of
water, oil and surfactant. As with Bose-Einstein condensation, the transition
occurs even in the absence of interactions.
Sear RP (1998) Phase separation and crystallisation of polydisperse hard spheres, Europhysics Letters 44 pp. 531-535
Hard spheres with a polydispersity above approximately 8% are shown to
crystallise into two phase-separated solid phases. A polydispersity above 8% is
too large to be tolerated by a single solid phase but phase separation produces
two fractions with polydispersities sufficiently narrow to allow them to
crystallise. It may not be possible to observe this in experiment due to the
intervention of a glass transition.
Sear RP (2006) Heterogeneous and homogeneous nucleation compared: Rapid nucleation on microscopic impurities, JOURNAL OF PHYSICAL CHEMISTRY B 110 (10) pp. 4985-4989 AMER CHEMICAL SOC
Che Abdullah CA, Asanithi P, Brunner EW, Sear RP, Dalton AB, Lewis Azad C, Ovalle-Robles R, Lima MD, Lepro X, Collins S, Baughman RH (2010) Cell patterning and alignment on nanostructured isotropic and anisotropic carbon nanotubes substrates, European Cells and Materials 20 (SUPPL.3) pp. 39-39
Sear RP (2007) Nucleation at contact lines where fluid-fluid interfaces meet solid surfaces, JOURNAL OF PHYSICS-CONDENSED MATTER 19 (46) ARTN 466106 IOP PUBLISHING LTD
Polydisperse mixtures are those in which components with a whole range of
sizes are present. It is shown that the fluid phase of polydisperse hard
spheres is thermodynamically unstable unless the density of large spheres
decreases at least exponentially as their size increases. The instability is
with respect to the large spheres crystallising out into multiple solid phases.
González-Pérez V, Schmierer B, Hill CS, Sear RP (2011) Studying Smad2 intranuclear diffusion dynamics by mathematical modelling of FRAP experiments., Integr Biol (Camb) 3 (3) pp. 197-207 RSC Publishing
We combine Fluorescence Recovery After Photobleaching (FRAP) experiments with mathematical modelling to study the dynamics inside the nucleus of both the TGF-²-sensitive transcriptional regulator Smad2, and Green-Fluorescent Protein (GFP). We show how combining modelling with bleaching strips of different areas allows a rigorous test of whether or not a protein is moving via diffusion as a single species. As noted recently by others, it is important to consider diffusion during the bleaching process. Neglecting it can cause serious error. Also, it is possible to use the bleaching process itself to provide an extra consistency test to the models predicting the recovery. With our method we show that the dynamics of GFP are consistent with it diffusing as a single species in a uniform environment in which flow is negligible. In contrast, the dynamics of the intracellular signal transducer Smad2 are never consistent with it moving as a single species via simple diffusion in a homogeneous environment without flow. Adding TGF-² slows down the dynamics of Smad2 but even without TGF-², the Smad2 dynamics are influenced by one or more of: association, flow, and inhomogeneity in space of the dynamics. We suggest that the dynamics inside cells of many proteins may be poorly described by simple diffusion of a single species, and that our methodology provides a general and powerful way to test this hypothesis.
Sear RP (2007) Nucleation: theory and applications to protein solutions and colloidal suspensions, JOURNAL OF PHYSICS-CONDENSED MATTER 19 (3) ARTN 033101 IOP PUBLISHING LTD
Recent experimental [Diao et al., J. Am. Chem. Soc. 2011 133, 3756.] and simulation results [Sear, J. Phys. Cond. Matt. 2012 24, 052205.] are not consistent with a nucleation rate that is in the thermodynamic limit. This has consequences, if the rate is not in the thermodynamic limit, the time for nucleation will not necessarily scale as one over system size. Here, I show how to analyze data for nucleation times to test for the existence of a well-defined nucleation rate. I also show how to estimate the scaling of the nucleation time with the number of nucleation sites. The prediction is that the farther the system is from the thermodynamic limit, the more rapidly the nucleation time varies with system size. To make this prediction, I use extreme-value statistics. I also show how nucleation data can be analyzed to extract information on the heterogeneity in the surfaces on which nucleation is occurring. © 2013 American Chemical Society.
The adsorption of polydisperse ideal polymer chains is shown to be sensitive
to the large N tail of the distribution of chains. If and only if the number of
chains decays more slowly than exponentially then there is an adsorption
transition like that of monodisperse infinite chains. If the number decays
exponentially the adsorption density diverges continuously at a temperature
which is a function of the mean chain length. At low coverages, chains with
repulsive monomer--monomer interactions show the same qualitative behaviour
Sear RP (1997) Depletion driven adsorption of colloidal rods onto a hard wall, Physical Review E
In a mixed suspension of rods and small polymer coils, the rods adsorb onto a
hard wall in contact with the suspension. This adsorption is studied in the low
density of rods limit. It is driven by depletion forces and is much stronger
for long rods than for spheres. This is shown by means of exact, numerical,
calculations and an approximate theory.
Sear RP (2012) Non-self-averaging nucleation rate due to quenched disorder, JOURNAL OF PHYSICS-CONDENSED MATTER 24 (5) ARTN 052205 IOP PUBLISHING LTD
Page AJ, Sear RP (2009) Crystallization Controlled by the Geometry of a Surface, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 131 (48) pp. 17550-17551 AMER CHEMICAL SOC
Utgenannt A, Maspero Ross, Fortini Andrea, Turner R, Florescu Marian, Jeynes Christopher, Kanaras AG, Muskens OL, Sear Richard, Keddie Joseph (2016) Fast Assembly of Gold Nanoparticles in Large-Area 2-D Nanogrids Using a One-Step, Near-Infrared Radiation-Assisted Evaporation Process, ACS Nano 10 (2) pp. 2232-2242
American Chemical Society
When fabricating photonic crystals from suspensions in volatile liquids using the horizontal deposition method, the conventional approach is to evaporate slowly to increase the time for particles to settle in an ordered, periodic close-packed structure. Here, we show that the greatest ordering of 10 nm aqueous gold nanoparticles (AuNPs) in a template of larger spherical polymer particles (mean diameter of 338 nm) is achieved with very fast water evaporation rates obtained with near-infrared radiative heating. Fabrication of arrays over areas of a few cm2 takes only seven minutes. The assembly process requires that the evaporation rate is fast relative to the particles? Brownian diffusion. Then a two-dimensional colloidal crystal forms at the falling surface, which acts as a sieve through which the AuNPs pass, according to our Langevin dynamics computer simulations. With sufficiently fast evaporation rates, we create a hybrid structure consisting of a two-dimensional AuNP nanoarray (or ?nanogrid?) on top of a three-dimensional polymer opal. The process is simple, fast and one-step. The interplay between the optical response of the plasmonic Au nanoarray and the microstructuring of the photonic opal results in unusual optical spectra with two extinction peaks, which are analyzed via finite-difference time-domain method simulations. Comparison between experimental and modelling results reveals a strong interplay of plasmonic modes and collective photonic effects, including the formation of a high-order stop band and slow-light enhanced plasmonic absorption. The structures, and hence their optical signatures, are tuned by adjusting the evaporation rate via the infrared power density.
In simulations and experiments, we study the drying of films containing mixtures of large and small colloidal particles in water. During drying, the mixture stratifies into a layer of the larger particles at the bottom with a layer of the smaller particles on top. We developed a model to show that a gradient in osmotic pressure, which develops dynamically during drying, is responsible for the segregation mechanism behind stratification.
Models without an explicit time dependence, called singular models, are widely used for fitting the distribution of temperatures at which water droplets freeze. In 1950 Levine developed the original singular model. His key assumption was that each droplet contained many nucleation sites, and that freezing occurred due to the nucleation site with the highest freezing temperature. The fact that freezing occurs due to the maximum value out of large number of nucleation temperatures, means that we can apply the results of what is called extreme-value statistics. This is the statistics of the extreme, i.e., maximum or minimum, value of a large number of random variables. Here we use the results of extreme-value statistics to show that we can generalise Levine's model to produce the most general singular model possible. We show that when a singular model is a good approximation, the distribution of freezing temperatures should always be given by what is called the generalised extreme-value distribution. In addition, we also show that the distribution of freezing temperatures for droplets of onesize, can be used to make predictions for the scaling of the median nucleation temperature with droplet size, and vice versa.
Using computational modelling, we investigate mechanisms of signal transduction focusing on
the spindle assembly checkpoint where a single unattached kinetochore is able to signal to prevent
cell cycle progression. This inhibitory signal switches off rapidly once spindle microtubules have
attached to all kinetochores. This requirement tightly constrains the possible mechanisms. Here
we investigate two possible mechanisms for spindle checkpoint operation in metazoan cells, both
supported by recent experiments. The first involves the free diffusion and sequestration of cell-cycle
regulators. This mechanism is severely constrained both by experimental fluorescence recovery
data and also by the large volumes involved in open mitosis in metazoan cells. Using a simple
mathematical analysis and computer simulation, we find that this mechanism can generate the
inhibition found in experiment but likely requires a two stage signal amplification cascade. The
second mechanism involves spatial gradients of a short-lived inhibitory signal that propagates first
by diffusion but then primarily via active transport along spindle microtubules. We propose that
both mechanisms may be operative in the metazoan spindle assembly checkpoint, with either able
to trigger anaphase onset even without support from the other pathway.
Nucleation of a new phase almost always starts at a surface. This surface is almost always assumed not to change with time. However, surfaces can roughen, partially dissolve and change chemically with time. Each of these irreversible changes will change the nucleation rate at the surface, resulting in a time-dependent nucleation rate. Here we use a simple model to show that partial surface dissolution can qualitatively change the nucleation process, in a way that is testable in experiment. The changing surface means that the nucleation rate is increasing with time. There is an initial period during which no nucleation occurs, followed by relatively rapid nucleation.
When films are deposited from mixtures of colloidal particles of two different sizes, a diverse range of functional structures can result. One structure of particular interest is a stratified film in which the top surface layer has a composition different than in the interior. Here, we explore the conditions under which a stratified layer of small particles develops spontaneously in a colloidal film that is cast from a binary mixture of small and large polymer particles that are suspended in water. A recent model, which considers the cross-interaction between the large and small particles (Zhou et al., Phys. Rev. Lett. (2017) 118, 108002), predicts that stratification will develop from dilute binary mixtures when the particle size ratio (a), initial volume fraction of small particles (f
s), and Péclet number are high. In experiments and Langevin dynamics simulations, we systematically vary a and fs in both dilute and concentrated suspensions. We find that stratified films develop when f
s is increased, which is in agreement with the model. In dilute suspensions, there is reasonable agreement between the experiments and the Zhou et al. model. In concentrated suspensions, stratification occurs in experiments only for the higher size ratio a = 7. Simulations using a high Péclet number, additionally find stratification with a = 2, when f
s is high enough. Our results provide a quantitative understanding of the conditions under which stratified colloidal films assemble. Our research has relevance for the design of coatings with targeted optical and mechanical properties at their surface.
Martin-Fabiani I, Fortini Andrea, Lesage de la Haye J, Koh ML, Taylor Spencer, Bourgeat-Lami E, Lansalot M, D?Agosto F, Sear Richard, Keddie Joseph (2016) pH-Switchable Stratification of Colloidal Coatings: Surfaces ?On Demand?, ACS Applied Materials and Interfaces 8 (50) pp. 34755-34761
American Chemical Society
Stratified coatings are used to provide properties at a surface, such as hardness or refractive index, which are different from underlying layers. Although time-savings are offered by self-assembly approaches, there have been no methods yet reported to offer stratification on demand. Here, we demonstrate a strategy to create self-assembled stratified coatings, which can be switched to homogenous structures when required. We use blends of large and small colloidal polymer particle dispersions in water that self-assemble during drying because of an osmotic pressure gradient that leads to a downward velocity of larger particles. Our confocal fluorescent microscopy images reveal a distinct surface layer created by the small particles. When the pH of the initial dispersion is raised, the hydrophilic shells of the small particles swell substantially, and the stratification is switched off. Brownian dynamics simulations explain the suppression of stratifi-cation when the small particles are swollen as a result of reduced particle mobility, a drop in the pressure gradient, and less time available before particle jamming. Our strategy paves the way for applications in antireflection films and pro-tective coatings in which the required surface composition can be achieved on demand, simply by adjusting the pH prior to deposition.
We advance the quantitative study of nucleation by combining the study of hundreds of samples, with statistical tests for reproducibility, and for well-defined nucleation rates. Unlike in most previous work, we find that in the samples that nucleate after the first hour of our experiment the equilibrium glycine polymorph predominates over the alpha form.
We investigate the drying process of three-component and polydisperse colloidal suspensions using Brownian dynamics simulations. We have previously reported (Phys. Rev. Lett. 2016, 116, 118301) on the drying of binary mixtures. For binary mixtures, we found that a gradient of colloidal osmotic pressure develops during drying and that this leads to the final film being stratified with a layer of smaller particles on top of a layer of larger particles. Here, we find that stratification by size is very general and also occurs in ternary and polydisperse mixtures. We name the segregation effect colloidal diffusiophoresis. In particular, we show that by changing the composition of a ternary mixture, different stratification morphologies can be achieved and hence the film properties can be tuned. In polydisperse spheres, colloidal diffusiophoresis leads to enrichment in the large particles at the bottom part of the film, whereas the top part is enriched with smaller particles. This segregation means that in the final film, the particle size distribution depends on height. Thus, the properties of the film will then depend on height. We propose a model that predicts a power-law dependence of the phoretic velocity on particle size. Results from the model and simulation show a good agreement
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 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 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.
We perform particle resolved experimental studies on the heterogeneous crystallisation process of two component
mixtures of hard spheres. The components have a size ratio of 0.39. We compared these with molecular
dynamics simulations of homogenous nucleation. We find for both experiments and simulations that the
final assemblies are interstitial solid solutions, where the large particles form crystalline close-packed lattices,
whereas the small particles occupy random interstitial sites. This interstitial solution resembles that found
at equilibrium when the size ratios are 0.3 [Filion et al., Phys. Rev. Lett. 107, 168302 (2011)] and 0.4
[Filion, PhD Thesis, Utrecht University (2011)]. However, unlike these previous studies, for our system simulations
showed that the small particles are trapped in the octahedral holes of the ordered structure formed
by the large particles, leading to long-lived non-equilibrium structures in the time scales studied and not the
equilibrium interstitial solutions found earlier. Interestingly, the percentage of small particles in the crystal
formed by the large ones rapidly reaches a maximum of 14% for most of the packing fractions tested, unlike
previous predictions where the occupancy of the interstitial sites increases with the system concentration.
Finally, no further hopping of the small particles was observed.
A colloidal particle placed in an inhomogeneous solution of smaller non-adsorbing polymers will
move towards regions of lower polymer concentration, in order to reduce the free energy of the
interface between the surface of the particle and the solution. This phenomenon is known as diffusiophoresis.
Treating the polymer as penetrable hard spheres, as in the Asakura-Oosawa model, a
simple analytic expression for the diffusiophoretic drift velocity can be obtained. In the context of
drying films we show that diffusiophoresis by this mechanism can lead to stratification under easily
accessible experimental conditions. By stratification we mean spontaneous formation of a layer of
polymer on top of a layer of the colloid. Transposed to the case of binary colloidal mixtures, this
offers an explanation for the stratification observed recently in these systems [A. Fortini et al., Phys.
Rev. Lett. 116, 118301 (2016)]. Our results emphasise the importance of treating solvent dynamics
explicitly in these problems, and caution against the neglect of hydrodynamic interactions or the
use of implicit solvent models in which the absence of solvent back
ow results in an unbalanced
osmotic force which gives rise to large but unphysical effects.
I model the drying of a liquid film containing small and big colloid particles. Fortini et al. [A. Fortini et al, Phys. Rev. Lett. 116, 118301 (2016)] studied these films with both computer simulation and experiment. They found that at the end of drying the mixture had stratified with a layer of the smaller particles on top of the big particles. I develop a simple model for this process. The model has two ingredients: arrest of the diffusion of the particles at high density, and diffusiophoretic motion of the big particles due to gradients in the concentration of the small particles. The model predicts that stratification only occurs over a range of initial concentrations of the smaller colloidal species. At concentrations that are either too low or too high, the concentration gradients due to drying are not enough to push the big particles away and so produce a layer at the top of only small particles. In agreement with earlier work, the model also predicts that large Peclet numbers for drying are needed to see stratification.
Crystallisation by precipitation is a very common technique in industry, however the crystals produced are often of poor quality, characterised by broad particle size distribution and morphological inhomogeneities. These problems can be overcome by the use of ultrasound. Sonocrystallisation, or ultrasound-assisted crystallisation, has already demonstrated its general benefits in terms of reduction in crystallisation time, smaller and more homogeneous crystals and repeatability. However, there are many issues still unaddressed, such as poor knowledge of the mechanism of sonocrystallisation and of the governing parameters of the whole system. This is largely attributed to lack of systematic studies, varying frequency and power while using the same equipment, as well as difficulties in comparing results from different systems. Furthermore, ultrasound is still considered uneconomical in industrial scale, due to its high energy demand. Therefore, there is the necessity of optimising the use of ultrasound for guaranteeing a high-quality product with the lowest energy consumption.
This thesis therefore focused on studying the effects of sonocrystallisation for two different crystallisation systems by precipitation: the antisolvent crystallisation of sodium chloride and the reactive crystallisation of ZIF-8, a type of Metal-Organic Frameworks (MOFs). In both systems, frequency, power and sonication time was systematically varied, and the effects on the product obtained investigated. The effect of changing supersaturation was also studied. The comparison between a simpler and a more complex system could help on obtaining general conclusions useful for clarifying the mechanism of sonocrystallisation.
The antisolvent sonocrystallisation of sodium chloride revealed that sonication caused a reduction of the crystal size up to 10 times with respect to unsonicated conditions. This was achieved within a few seconds of sonication (5 s for high supersaturation and 15 s for low supersaturation), indicating that the effects of ultrasound were on the nucleation, causing the rapid formation of small and regular crystals. Phenomena of sono-fracture was excluded because the crystals formed were morphologically regular, very different from fragments. Adding a subsequent step in silent conditions or using intermittent ultrasound bursts coupled with silent conditions showed a limited crystal growth. Hence, ultrasound uses the majority of the solute forming new small crystals and leaving in the solution only a small amount of sodium chloride. The effects of different frequencies and powers were more evident at lower supersaturations, with lower frequency being more effective at reducing crystal size. However, under these conditions, although a small average crystal size was obtained, the particle size distributions were bimodal at low power. At high supersaturation, this bimodality disappeared even at low powers.
For the reactive crystallisation of ZIF-8 at high excess of ligand, it was confirmed that the action of ultrasound caused a reduction of the crystal size up to nanometre. Furthermore, it was demonstrated again that the action of sonication was on the early stages of the crystallisation. However, the effects of ultrasound resembled a lot the results obtained when only mixing was applied, suggesting that sonication was not directly influencing the chemistry of the reaction. In addition, the BET surface area appeared to be related to the power used, reaching a maximum and decreasing beyond a certain power. This suggests that a competition between micromixing, causing an increase of the BET surface area, and shockwaves, responsible of breaking the framework during its formation. On the other hand, when a low excess of ligand was used, it was revealed that the formation of by-products was accelerated when mixing or sonication were applied. However, if shorter reaction time was applied, it was possible to obtain a reasonable quality of ZIF-8 at low
This paper reports for the first time the development in the size and shape of sodium chloride crystals during the anti-solvent crystallization in ethanol under different sonication modes. Sonication using 98 kHz and calorimetric power of 6 W was applied either continuously for a range of crystallisation times (5 ? 90 s) or intermittently (5 s pulse). Under silent conditions, crystallization time of 90 s generated crystals with an average size of 73.8 ± 6.9 ¼m, compared to 8.7 ± 2.8 ¼m under 90 s of continuous sonication. However, it was observed that within the first 5 s of sonication at the beginning of the crystallization, the average crystal size was already reduced to 7.0 ± 3.3 ¼m. If the system was left to crystallise further to 90 s without ultrasound, the crystal size grew only slightly to 8.2 ± 1.4 ¼m. When 5 s burst of ultrasound was applied during the crystallization process, a bimodal distribution of small (from sonication) and large crystals (from the silent period) was obtained. These results imply that the major influence of sonication is crystal nucleation rather than fragmentation, and equilibrium is reached with 5 s sonication by precipitating most of the crystals in solution.
The more we learn about the cytoplasm of cells, the more we realise that the cytoplasm is not
uniform but instead is highly inhomogeneous. In any inhomogeneous solution, there are concentration gradients, and particles move either up or down these gradients due to a mechanism called diffusiophoresis. I estimate that inside metabolically active cells, the dynamics of particles can be strongly accelerated by diffusiophoresis, provided that they are at least tens of nanometres across. The dynamics of smaller objects, such as single proteins are largely unaffected.
Sonocrystallisation is the application of ultrasound to the crystallisation process. The benefits obtained by sonication have been widely studied since the beginning of the 20th century and so far it is clear that ultrasound can be a very useful tool for enhancing crystallisation and controlling the properties of the final product. Crystal size, polymorphs, purity, process repeatability and lower induction time are only some of the advantages of sonocrystallisation. Even though the effects of sonication on crystallisation are quite clear, the physical explanation of the phenomena involved is still lacking. Is the presence of cavitation necessary for the process? Or is only the bubbles surface responsible for enhancing crystallisation? Are the strong local increases in pressure and temperature induced by cavitation the main cause of all the observed effects? Or is it the strong turbulence induced in the system, instead? Many questions still remain and can only be appreciated with an understanding of the complexity behind the individual processes of crystallisation and acoustic cavitation. Therefore, this review will first summarise the theories behind crystallisation and acoustic cavitation, followed by a description of all the current proposed sonocrystallisation mechanisms, and conclude with an overview on future prospects of sonocrystallisation applications.