106 research outputs found
Electrokinetic and hydrodynamic properties of charged-particles systems: From small electrolyte ions to large colloids
Dynamic processes in dispersions of charged spherical particles are of
importance both in fundamental science, and in technical and bio-medical
applications. There exists a large variety of charged-particles systems,
ranging from nanometer-sized electrolyte ions to micron-sized charge-stabilized
colloids. We review recent advances in theoretical methods for the calculation
of linear transport coefficients in concentrated particulate systems, with the
focus on hydrodynamic interactions and electrokinetic effects. Considered
transport properties are the dispersion viscosity, self- and collective
diffusion coefficients, sedimentation coefficients, and electrophoretic
mobilities and conductivities of ionic particle species in an external electric
field. Advances by our group are also discussed, including a novel
mode-coupling-theory method for conduction-diffusion and viscoelastic
properties of strong electrolyte solutions. Furthermore, results are presented
for dispersions of solvent-permeable particles, and particles with non-zero
hydrodynamic surface slip. The concentration-dependent swelling of ionic
microgels is discussed, as well as a far-reaching dynamic scaling behavior
relating colloidal long- to short-time dynamics
Collective diffusion in charge-stabilized suspensions: Concentration and salt effects
The authors present a joint experimental-theoretical study of collective diffusion properties in aqueous suspensions of charge-stabilized fluorinated latex spheres. Small-angle x-ray scattering and x-ray photon correlation spectroscopy have been used to explore the concentration and ionic-strength dependence of the static and short-time dynamic properties including the hydrodynamic function H (q), the wave-number-dependent collective diffusion coefficient D (q), and the intermediate scattering function over the entire accessible range. They show that all experimental data can be quantitatively described and explained by means of a recently developed accelerated Stokesian dynamics simulation method, in combination with a modified hydrodynamic many-body theory. In particular, the behavior of H (q) for de-ionized and dense suspensions can be attributed to the influence of many-body hydrodynamics, without any need for postulating hydrodynamic screening to be present, as it was done in earlier work. Upper and lower boundaries are provided for the peak height of the hydrodynamic function and for the short-time self-diffusion coefficient over the entire range of added salt concentrations.Fil: Gapinski, J.. A. Mickiewicz University; PoloniaFil: Patkowski, A.. A. Mickiewicz University; PoloniaFil: Banchio, Adolfo Javier. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Física Enrique Gaviola. Universidad Nacional de Córdoba. Instituto de Física Enrique Gaviola; ArgentinaFil: Holmqvist, P.. Helmholtz Gemeinschaft. Forschungszentrum Jülich; AlemaniaFil: Meier, Guillermo Enrique. Helmholtz Gemeinschaft. Forschungszentrum Jülich; AlemaniaFil: Lettinga, M.P.. Helmholtz Gemeinschaft. Forschungszentrum Jülich; AlemaniaFil: Nägele, G.. Helmholtz Gemeinschaft. Forschungszentrum Jülich; Alemani
Polymers with attractive interactions on the Husimi tree
We obtain the solution of models of self-avoiding walks with attractive
interactions on Husimi lattices built with squares. Two attractive interactions
are considered: between monomers on first-neighbor sites and not consecutive
along a walk and between bonds located on opposite edges of elementary squares.
For coordination numbers q>4, two phases, one polymerized the other
non-polymerized, are present in the phase diagram. For small values of the
attractive interaction the transition between those phases is continuous, but
for higher values a first-order transition is found. Both regimes are separated
by a tricritical point. For q=4 a richer phase diagram is found, with an
additional (dense) polymerized phase, which is stable for for sufficiently
strong interactions between bonds. The phase diagram of the model in the
three-dimensional parameter space displays surfaces of continuous and
discontinuous phase transitions and lines of tricritical points, critical
endpoints and triple points.Comment: 7 pages, 6 figure
Hydrodynamic interactions in colloidal ferrofluids: A lattice Boltzmann study
We use lattice Boltzmann simulations, in conjunction with Ewald summation
methods, to investigate the role of hydrodynamic interactions in colloidal
suspensions of dipolar particles, such as ferrofluids. Our work addresses
volume fractions of up to 0.20 and dimensionless dipolar interaction
parameters of up to 8. We compare quantitatively with Brownian
dynamics simulations, in which many-body hydrodynamic interactions are absent.
Monte Carlo data are also used to check the accuracy of static properties
measured with the lattice Boltzmann technique. At equilibrium, hydrodynamic
interactions slow down both the long-time and the short-time decays of the
intermediate scattering function , for wavevectors close to the peak of
the static structure factor , by a factor of roughly two. The long-time
slowing is diminished at high interaction strengths whereas the short-time
slowing (quantified via the hydrodynamic factor ) is less affected by the
dipolar interactions, despite their strong effect on the pair distribution
function arising from cluster formation. Cluster formation is also studied in
transient data following a quench from ; hydrodynamic interactions
slow the formation rate, again by a factor of roughly two
Rational design of benzobisheterocycle metallo-β-lactamase inhibitors:a tricyclic scaffold enhances potency against target enzymes
Antimicrobial resistance is a global public health threat. Metallo-β-lactamases (MBLs) inactivate β-lactam antibiotics, including carbapenems, are disseminating among Gram-negative bacteria, and lack clinically useful inhibitors. The evolving bisthiazolidine (BTZ) scaffold inhibits all three MBL subclasses (B1 - B3). We report design, synthesis and evaluation of BTZ analogs. Structure-activity relationships identified the BTZ thiol as essential, while the carboxylate is replaceable, with its removal enhancing potency by facilitating hydrophobic interactions within the MBL active site. While the introduction of a flexible aromatic ring is neutral or detrimental for inhibition, a rigid (fused) ring generated nM benzobisheterocycle (BBH) inhibitors that potentiated carbapenems against MBL-producing strains. Crystallography of BBH:MBL complexes identified hydrophobic interactions as the basis of potency towards B1 MBLs. These data underscore BTZs as versatile, potent broad spectrum MBL inhibitors (with activity extending to enzymes refractory to other inhibitors), and provide a rational approach to further improve the tricyclic BBH scaffold
2-Mercaptomethyl-thiazolidines use conserved aromatic-S interactions to achieve broad-range inhibition of metallo-β-lactamases
Infections caused by multidrug resistant (MDR) bacteria are a major public health threat. Carbapenems are among the most potent antimicrobial agents that are commercially available to treat MDR bacteria. Bacterial production of carbapenem-hydrolysing metallo-b-lactamases (MBLs) challenges their safety and efficacy, with subclass B1 MBLs hydrolysing almost all b-lactam antibiotics. MBL inhibitors would fulfil an urgent clinical need by prolonging the lifetime of these life-saving drugs. Here we report the synthesis and activity of a series of 2-mercaptomethyl-thiazolidines (MMTZs), designed to replicate MBL interactions with reaction intermediates or hydrolysis products. MMTZs are potent competitive inhibitors of B1 MBLs in vitro (e.g., Ki ¼ 0.44 mM vs. NDM-1). Crystal structures of MMTZ complexes reveal similar binding patterns to the most clinically important B1 MBLs (NDM-1, VIM-2 and IMP-1), contrasting with previously studied thiol-based MBL inhibitors, such as bisthiazolidines (BTZs) or captopril stereoisomers, which exhibit lower, more variable potencies and multiple binding modes. MMTZ binding involves thiol coordination to the Zn(II) site and extensive hydrophobic interactions, burying the inhibitor more deeply within the active site than D/L-captopril. Unexpectedly, MMTZ binding features a thioether–p interaction with a conserved active-site aromatic residue, consistent with their equipotent inhibition and similar binding to multiple MBLs. MMTZs penetrate multiple Enterobacterales, inhibit NDM-1 in situ, and restore carbapenem potency against clinical isolates expressing B1 MBLs. Based on their inhibitory profile and lack of eukaryotic cell toxicity, MMTZs represent a promising scaffold for MBL inhibitor development. These results also suggest sulphur–p interactions can be exploited for general ligand design in medicinal chemistry
Increased Terpenoid Accumulation in Cotton (Gossypium hirsutum) Foliage is a General Wound Response
The subepidermal pigment glands of cotton accumulate a variety of terpenoid products, including monoterpenes, sesquiterpenes, and terpenoid aldehydes that can act as feeding deterrents against a number of insect herbivore species. We compared the effect of herbivory by Spodoptera littoralis caterpillars, mechanical damage by a fabric pattern wheel, and the application of jasmonic acid on levels of the major representatives of the three structural classes of terpenoids in the leaf foliage of 4-week-old Gossypium hirsutum plants. Terpenoid levels increased successively from control to mechanical damage, herbivory, and jasmonic acid treatments, with E-β-ocimene and heliocide H1 and H4 showing the highest increases, up to 15-fold. Herbivory or mechanical damage to older leaves led to terpenoid increases in younger leaves. Leaf-by-leaf analysis of terpenes and gland density revealed that higher levels of terpenoids were achieved by two mechanisms: (1) increased filling of existing glands with terpenoids and (2) the production of additional glands, which were found to be dependent on damage intensity. As the relative response of individual terpenoids did not differ substantially among herbivore, mechanical damage, and jasmonic acid treatments, the induction of terpenoids in cotton foliage appears to represent a non-specific wound response mediated by jasmonic acid
Lattice Boltzmann simulations of soft matter systems
This article concerns numerical simulations of the dynamics of particles
immersed in a continuum solvent. As prototypical systems, we consider colloidal
dispersions of spherical particles and solutions of uncharged polymers. After a
brief explanation of the concept of hydrodynamic interactions, we give a
general overview over the various simulation methods that have been developed
to cope with the resulting computational problems. We then focus on the
approach we have developed, which couples a system of particles to a lattice
Boltzmann model representing the solvent degrees of freedom. The standard D3Q19
lattice Boltzmann model is derived and explained in depth, followed by a
detailed discussion of complementary methods for the coupling of solvent and
solute. Colloidal dispersions are best described in terms of extended particles
with appropriate boundary conditions at the surfaces, while particles with
internal degrees of freedom are easier to simulate as an arrangement of mass
points with frictional coupling to the solvent. In both cases, particular care
has been taken to simulate thermal fluctuations in a consistent way. The
usefulness of this methodology is illustrated by studies from our own research,
where the dynamics of colloidal and polymeric systems has been investigated in
both equilibrium and nonequilibrium situations.Comment: Review article, submitted to Advances in Polymer Science. 16 figures,
76 page
Chrysolina herbacea Modulates Terpenoid Biosynthesis of Mentha aquatica L.
Interactions between herbivorous insects and plants storing terpenoids are poorly
understood. This study describes the ability of Chrysolina
herbacea to use volatiles emitted by undamaged Mentha
aquatica plants as attractants and the plant's response to
herbivory, which involves the production of deterrent molecules. Emitted plant
volatiles were analyzed by GC-MS. The insect's response to plant volatiles
was tested by Y-tube olfactometer bioassays. Total RNA was extracted from
control plants, mechanically damaged leaves, and leaves damaged by herbivores.
The terpenoid quantitative gene expressions (qPCR) were then assayed. Upon
herbivory, M. aquatica synthesizes and emits
(+)-menthofuran, which acts as a deterrent to C. herbacea.
Herbivory was found to up-regulate the expression of genes involved in terpenoid
biosynthesis. The increased emission of (+)-menthofuran was correlated with
the upregulation of (+)-menthofuran synthase
Diffusion in crowded biological environments: applications of Brownian dynamics
Biochemical reactions in living systems occur in complex, heterogeneous media with total concentrations of macromolecules in the range of 50 - 400 mgml. Molecular species occupy a significant fraction of the immersing medium, up to 40% of volume. Such complex and volume-occupied environments are generally termed 'crowded' and/or 'confined'. In crowded conditions non-specific interactions between macromolecules may hinder diffusion - a major process determining metabolism, transport, and signaling. Also, the crowded media can alter, both qualitatively and quantitatively, the reactions in vivo in comparison with their in vitro counterparts. This review focuses on recent developments in particle-based Brownian dynamics algorithms, their applications to model diffusive transport in crowded systems, and their abilities to reproduce and predict the behavior of macromolecules under in vivo conditions
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