287 research outputs found
Conformational control of Pd2L4 assemblies with unsymmetrical ligands
With increasing interest in the potential utility of metallo-supramolecular architectures for applications as diverse as catalysis and drug delivery, the ability to develop more complex assemblies is keenly sought after. Despite this, symmetrical ligands have been utilised almost exclusively to simplify the self-assembly process as without a significant driving foa mixture of isomeric products will be obtained. Although a small number of unsymmetrical ligands have been shown to serendipitously form well-defined metallo-supramolecular assemblies, a more systematic study could provide generally applicable information to assist in the design of lower symmetry architectures. Pd2L4 cages are a popular class of metallo-supramolecular assembly; research seeking to introduce added complexity into their structure to further their functionality has resulted in a handful of examples of heteroleptic structures, whilst the use of unsymmetrical ligands remains underexplored. Herein we show that it is possible to design unsymmetrical ligands in which either steric or geometric constraints, or both, can be incorporated into ligand frameworks to ensure exclusive formation of single isomers of three-dimensional Pd2L4 metallo-supramolecular assemblies with high fidelity. In this manner it is possible to access Pd2L4 cage architectures of reduced symmetry, a concept that could allow for the controlled spatial segregation of different functionalities within these systems. The introduction of steric directing groups was also seen to have a profound effect on the cage structures, suggesting that simple ligand modifications could be used to engineer structural properties
Mode-coupling theory predictions for a limited valency attractive square-well model
Recently we have studied, using numerical simulations, a limited valency
model, i.e. an attractive square well model with a constraint on the maximum
number of bonded neighbors. Studying a large region of temperatures and
packing fractions , we have estimated the location of the liquid-gas
phase separation spinodal and the loci of dynamic arrest, where the system is
trapped in a disordered non-ergodic state. Two distinct arrest lines for the
system are present in the system: a {\it (repulsive) glass} line at high
packing fraction, and a {\it gel} line at low and . The former is
essentially vertical (-controlled), while the latter is rather horizontal
(-controlled) in the plane. We here complement the molecular
dynamics results with mode coupling theory calculations, using the numerical
structure factors as input. We find that the theory predicts a repulsive glass
line -- in satisfactory agreement with the simulation results -- and an
attractive glass line which appears to be unrelated to the gel line.Comment: 12 pages, 6 figures. To appear in J. Phys. Condens. Matter, special
issue: "Topics in Application of Scattering Methods for Investigation of
Structure and Dynamics of Soft Condensed Matter", Fiesole, November 200
2-Phenyl-4H-3,1-benzoxazin-4-one
The title molecule, C14H9NO2, is nearly planar with a dihedral angle of 3.72 (4)° beteewn the plane of the phenyl ring and the 3,1-benzoxazin-4-one fragment. The molecules are arranged into stacks parallel to the b axis via π–π stacking interactions [centroid-centroid distance = 4.2789 (11) Å] and the crystal packing is additionally stabilized by weak intermolecular C—H⋯O interactions
Columnar and lamellar phases in attractive colloidal systems
In colloidal suspensions, the competition between attractive and repulsive
interactions gives rise to a rich and complex phenomenology. Here, we study the
equilibrium phase diagram of a model system using a DLVO interaction potential
by means of molecular dynamics simulations and a thermodynamical approach. As a
result, we find tubular and lamellar phases at low volume fraction. Such
phases, extremely relevant for designing new materials, may be not easily
observed in the experiments because of the long relaxation times and the
presence of defects.Comment: 5 pages, 5 figure
Field-tuned order by disorder in frustrated Ising magnets with antiferromagnetic interactions
We demonstrate the appearance of thermal order by disorder in Ising pyrochlores with staggered antiferromagnetic order frustrated by an applied magnetic field. We use a mean-field cluster variational method, a low-temperature expansion, and Monte Carlo simulations to characterize the order-by-disorder transition. By direct evaluation of the density of states, we quantitatively show how a symmetry-broken state is selected by thermal excitations. We discuss the relevance of our results to experiments in 2D and 3D samples and evaluate how anomalous finite-size effects could be exploited to detect this phenomenon experimentally in two-dimensional artificial systems, or in antiferromagnetic all-in-all-out pyrochlores like Nd2Hf2O7 or Nd2Zr2O7, for the first time.Publisher PDFPeer reviewe
Field-tuned order by disorder in frustrated ising magnets with antiferromagnetic interactions
We demonstrate the appearance of thermal order by disorder in Ising pyrochlores with staggered antiferromagnetic order frustrated by an applied magnetic field. We use a mean-field cluster variational method, a low-temperature expansion, and Monte Carlo simulations to characterize the order-by-disorder transition. By direct evaluation of the density of states, we quantitatively show how a symmetry-broken state is selected by thermal excitations. We discuss the relevance of our results to experiments in 2D and 3D samples and evaluate how anomalous finite-size effects could be exploited to detect this phenomenon experimentally in two-dimensional artificial systems, or in antiferromagnetic all-in-all-out pyrochlores like Nd2Hf2O7 or Nd2Zr2O7, for the first time.Facultad de Ciencias ExactasInstituto de Física de Líquidos y Sistemas Biológico
The Valence Bond Glass phase
We show that a new glassy phase can emerge in presence of strong magnetic
frustration and quantum fluctuations. It is a Valence Bond Glass. We study its
properties solving the Hubbard-Heisenberg model on a Bethe lattice within the
large limit introduced by Affleck and Marston. We work out the phase
diagram that contains Fermi liquid, dimer and valence bond glass phases. This
new glassy phase has no electronic or spin gap (although a pseudo-gap is
observed), it is characterized by long-range critical valence bond correlations
and is not related to any magnetic ordering. As a consequence it is quite
different from both valence bond crystals and spin glasses
Protein surface functionalisation as a general strategy for facilitating biomimetic mineralisation of ZIF-8
The durability of enzymes in harsh conditions can be enhanced by encapsulation within metal-organic frameworks (MOFs) via a process called biomimetic mineralisation. Herein we show that the surface charge and chemistry of a protein determines its ability to seed MOF growth. We demonstrate that chemical modification of amino acids on the protein surface is an effective method for systematically controlling biomimetic mineralisation by zeolitic imidazolate framework-8 (ZIF-8). Reaction of surface lysine residues with succinic (or acetic) anhydride facilitates biomimetic mineralisation by increasing the surface negative charge, whereas reaction of surface carboxylate moieties with ethylenediamine affords a more positively charged protein and hinders the process. Moreover, computational studies confirm that the surface electrostatic potential of a protein is a good indicator of its ability to induce biomimetic mineralisation. This study highlights the important role played by protein surface chemistry in encapsulation and outlines a general method for facilitating the biomimetic mineralisation of proteins
Oversampling and replacement strategies in propensity score matching: a critical review focused on small sample size in clinical settings
Atrial fibrillation after orthotopic heart transplantatation: Pathophysiology and clinical impact
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