Dynamical scaling in fractal structures in the aggregation of tetraethoxysilane-derived sonogels

2010 ◽  
Vol 43 (5) ◽  
pp. 949-954 ◽  
Author(s):  
Dimas R. Vollet ◽  
Dario A. Donatti ◽  
Alberto Ibañez Ruiz ◽  
Fabio S. de Vicente
Keyword(s):  
Factor Model ◽  
Fractal Structures ◽  
Saxs Data ◽  
Scaling Properties ◽  
Dynamical Scaling ◽  
X Ray Scattering ◽  
Linear Chains ◽  
Saxs Intensity ◽  
Scattering Factor ◽  
Kinetics Of

Dynamical scaling properties in fractal structures were investigated from small-angle X-ray scattering (SAXS) data of the kinetics of aggregation in silica-based gelling systems. For lack of a maximum in the SAXS intensity curves, a characteristic correlation distance ξ was evaluated by fitting a particle scattering factor model valid for polydisperse coils of linear chains andf-functional branched polycondensates in solution, so the intensity atq= ξ−1,I(ξ−1,t), was considered to probe dynamical scaling properties. The following properties have been found: (i) the SAXS intensities corresponding to different timest,I(q,t), are given by a time-independent functionF(qξ) =I(q,t)ξ−D/Q, where the scattering invariantQhas been found to be time-independent; (ii) ξ exhibited a power-law behavior with time as ξ ≃tα, the exponent α being close to 1 but diminishing with temperature; (iii)I(ξ−1,t) exhibited a time dependence given byI(ξ−1,t) ≃tβ, with the exponent β found to be around 2 but diminishing with temperature, following the same behavior as the exponent α. In all cases, β/α was quite close to the fractal dimensionDat the end of the studied process. This set of findings is in notable agreement with the dynamical scaling properties.

Structure and aggregation kinetics of vinyltriethoxysilane-derived organic/silica hybrids

2010 ◽  
Vol 43 (5) ◽  
pp. 1005-1011 ◽  
Author(s):  
Dimas R. Vollet ◽  
Dario A. Donatti ◽  
Carlos M. Awano ◽  
William Chiappim ◽  
Marcio R. Vicelli ◽  
...  
Keyword(s):  
Basic Medium ◽  
Aggregation Kinetics ◽  
Debye Function ◽  
Phase Coarsening ◽  
X Ray Scattering ◽  
Time Scaling ◽  
Linear Chains ◽  
Saxs Intensity ◽  
Kinetics Of ◽  
Organic Silica

The aggregation kinetics of solutions of vinyltriethoxysilane-derived organic/silica hybrid species were studied by small-angle X-ray scattering (SAXS) in a strongly basic medium. The SAXS intensity was analysed by a modified Sharp–Bloomfield (SB) global function and its evolution was found to be compatible with the growth, coiling and branching of the polymeric macromolecules in solution. A form factor valid for randomly and nonrandomly branched polycondensates and for polydisperse coils of linear chains was used in the modified SB model, instead of the Debye function valid for monodisperse coils of linear chains. The aggregation kinetics are accelerated with increasing base concentration in the studied range, but all the kinetics curves can be matched to a unique curve using an appropriate time scaling factor. The aggregation kinetics suggest that physical forces (hydrothermal forces) associated with phase coarsening could be active in the aggregation process, together with diffusion mechanisms.

Rod-like particles growing in sol–gel processing of 1:1 molar mixtures of 3-glycidoxypropyltrimethoxysilane and tetraethoxysilane

2017 ◽  
Vol 50 (2) ◽  
pp. 489-497
Author(s):  
Dimas Roberto Vollet ◽  
Luiz Antonio Barreiro ◽  
Carlos Miranda Awano ◽  
Fabio Simões de Vicente ◽  
Makoto Yoshida ◽  
...  
Keyword(s):  
Initial Period ◽  
Sol Gel ◽  
Particle Growth ◽  
Fixed Number ◽  
Radius Of Gyration ◽  
Saxs Data ◽  
Advanced Degrees ◽  
X Ray Scattering ◽  
Saxs Intensity ◽  
Gel Processing

The growth kinetics and the structure of organic/silica hybrids prepared from acid hydrolysis of 1:1 molar mixtures of 3-glycidoxypropyltrimethoxysilane and tetraethoxysilane were studied by small-angle X-ray scattering (SAXS) at 315, 325 and 335 K. The evolution of the SAXS intensity is compatible with the growth of silica-rich domains by aggregation from a fixed number of primary particles. Two distinct growth regimes could be identified by analyzing the relation I(0) ∝ R g D between the intensity extrapolated to zero I(0), the radius of gyration R g of the aggregates and the exponent D, which gives information on the geometry and the mechanism of growth of the aggregates. An initial period was attributed to the growth of rod-like particles with approximately the same radius and variable length. At more advanced degrees of aggregation the process was controlled by the growth of larger aggregates with higher-order dimensionality. A narrow distribution of cylinder lengths given by the Schulz function fitted the experimental SAXS data well during the most part of the initial regime of cylindrical particle growth. These particles were later found as rod-like subunits of the larger aggregates grown at more advanced degrees of aggregation. Some condensation possibilities yielding the formation of structures compatible with those inferred from the present study are discussed.

In situ Time-Resolved Small-Angle X-ray Scattering Reveals the Formation Kinetics of Polyelectrolyte Complex Micelles

2019 ◽  
Author(s):  
Hao Wu ◽  
Jeffrey Ting ◽  
Siqi Meng ◽  
Matthew Tirrell
Keyword(s):  
Small Angle ◽  
Self Assembly ◽  
Electrostatic Interactions ◽  
Polyelectrolyte Complex ◽  
Time Resolved ◽  
X Ray ◽  
X Ray Scattering ◽  
Kinetics Of ◽  
Ray Scattering

We have directly observed the <i>in situ</i> self-assembly kinetics of polyelectrolyte complex (PEC) micelles by synchrotron time-resolved small-angle X-ray scattering, equipped with a stopped-flow device that provides millisecond temporal resolution. This work has elucidated one general kinetic pathway for the process of PEC micelle formation, which provides useful physical insights for increasing our fundamental understanding of complexation and self-assembly dynamics driven by electrostatic interactions that occur on ultrafast timescales.

scholarly journals Kinetics of Network Formation and Heterogeneous Dynamics of an Egg White Gel Revealed by Coherent X-Ray Scattering

2021 ◽  
Vol 126 (9) ◽  
Author(s):  
Nafisa Begam ◽  
Anastasia Ragulskaya ◽  
Anita Girelli ◽  
Hendrik Rahmann ◽  
Sivasurender Chandran ◽  
...  
Keyword(s):  
Network Formation ◽  
Egg White ◽  
X Ray ◽  
X Ray Scattering ◽  
Heterogeneous Dynamics ◽  
Kinetics Of ◽  
Ray Scattering

scholarly journals Controlling the Kinetics of an Enzymatic Reaction through Enzyme or Substrate Confinement into Lipid Mesophases with Tunable Structural Parameters

2020 ◽  
Vol 21 (14) ◽  
pp. 5116
Author(s):  
Marco Mendozza ◽  
Arianna Balestri ◽  
Costanza Montis ◽  
Debora Berti
Keyword(s):  
Reaction Kinetics ◽  
Self Assembly ◽  
Liquid Crystalline ◽  
Structural Parameters ◽  
Enzymatic Reaction ◽  
X Ray Scattering ◽  
Nitrophenyl Phosphate ◽  
Vis Spectroscopy ◽  
Kinetics Of ◽  
Enzyme Alkaline Phosphatase

Lipid liquid crystalline mesophases, resulting from the self-assembly of polymorphic lipids in water, have been widely explored as biocompatible drug delivery systems. In this respect, non-lamellar structures are particularly attractive: they are characterized by complex 3D architectures, with the coexistence of hydrophobic and hydrophilic regions that can conveniently host drugs of different polarities. The fine tunability of the structural parameters is nontrivial, but of paramount relevance, in order to control the diffusive properties of encapsulated active principles and, ultimately, their pharmacokinetics and release. In this work, we investigate the reaction kinetics of p-nitrophenyl phosphate conversion into p-nitrophenol, catalysed by the enzyme Alkaline Phosphatase, upon alternative confinement of the substrate and of the enzyme into liquid crystalline mesophases of phytantriol/H2O containing variable amounts of an additive, sucrose stearate, able to swell the mesophase. A structural investigation through Small-Angle X-ray Scattering, revealed the possibility to finely control the structure/size of the mesophases with the amount of the included additive. A UV–vis spectroscopy study highlighted that the enzymatic reaction kinetics could be controlled by tuning the structural parameters of the mesophase, opening new perspectives for the exploitation of non-lamellar mesophases for confinement and controlled release of therapeutics.

Structural refinement by restrained molecular-dynamics algorithm with small-angle X-ray scattering constraints for a biomolecule

2004 ◽  
Vol 37 (1) ◽  
pp. 103-109 ◽  
Author(s):  
Masaki Kojima ◽  
Alexander A. Timchenko ◽  
Junichi Higo ◽  
Kazuki Ito ◽  
Hiroshi Kihara ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Molecular Dynamics ◽  
Small Angle ◽  
Protein Structures ◽  
Saxs Data ◽  
X Ray ◽  
X Ray Scattering ◽  
Saxs Curve ◽  
Restrained Molecular Dynamics ◽  
Ray Scattering

A new algorithm to refine protein structures in solution from small-angle X-ray scattering (SAXS) data was developed based on restrained molecular dynamics (MD). In the method, the sum of squared differences between calculated and observed SAXS intensities was used as a constraint energy function, and the calculation was started from given atomic coordinates, such as those of the crystal. In order to reduce the contribution of the hydration effect to the deviation from the experimental (objective) curve during the dynamics, and purely as an estimate of the efficiency of the algorithm, the calculation was first performed assuming the SAXS curve corresponding to the crystal structure as the objective curve. Next, the calculation was carried out with `real' experimental data, which yielded a structure that satisfied the experimental SAXS curve well. The SAXS data for ribonuclease T1, a single-chain globular protein, were used for the calculation, along with its crystal structure. The results showed that the present algorithm was very effective in the refinement and adjustment of the initial structure so that it could satisfy the objective SAXS data.

scholarly journals Structural Analysis of the Partially Disordered Protein EspK from Mycobacterium tuberculosis

Crystals ◽  
2020 ◽  
Vol 11 (1) ◽  
pp. 18
Author(s):  
Abril Gijsbers ◽  
Nuria Sánchez-Puig ◽  
Ye Gao ◽  
Peter J. Peters ◽  
Raimond B. G. Ravelli ◽  
...  
Keyword(s):  
Host Response ◽  
Limited Proteolysis ◽  
Maximal Dimension ◽  
Globular Domain ◽  
Saxs Data ◽  
X Ray ◽  
Disordered Protein ◽  
X Ray Scattering ◽  
C Terminus ◽  
New Treatments

For centuries, tuberculosis has been a worldwide burden for human health, and gaps in our understanding of its pathogenesis have hampered the development of new treatments. ESX-1 is a complex machinery responsible for the secretion of virulence factors that manipulate the host response. Despite the importance of these secreted proteins for pathogenicity, only a few of them have been structurally and functionally characterised. Here, we describe a structural study of the ESX-secretion associated protein K (EspK), a 74 kDa protein known to be essential for the secretion of other substrates and the cytolytic effects of ESX-1. Small-Angle X-ray Scattering (SAXS) data show that EspK is a long molecule with a maximal dimension of 228 Å. It consists of two independent folded regions at each end of the protein connected by a flexible unstructured region driving the protein to coexist as an ensemble of conformations. Limited proteolysis identified a 26 kDa globular domain at the C-terminus of the protein consisting of a mixture of α-helices and β-strands, as shown by circular dichroism (CD) and SAXS. In contrast, the N-terminal portion is mainly helical with an elongated shape. Sequence conservation suggests that this architecture is preserved amongst the different mycobacteria species, proposing specific roles for the N- and C-terminal domains assisted by the middle flexible linker.

Kinetics of Ion-Exchange Reactions in Hybrid Organic–Inorganic Perovskite Thin Films Studied by In Situ Real-Time X-ray Scattering

2018 ◽  
Vol 9 (23) ◽  
pp. 6750-6754 ◽  
Author(s):  
Alessandro Greco ◽  
Alexander Hinderhofer ◽  
M. Ibrahim Dar ◽  
Neha Arora ◽  
Jan Hagenlocher ◽  
...  
Keyword(s):  
Thin Films ◽  
Ion Exchange ◽  
Real Time ◽  
Exchange Reactions ◽  
Inorganic Perovskite ◽  
X Ray ◽  
X Ray Scattering ◽  
Kinetics Of ◽  
Kinetics Of Ion Exchange

Fractal aggregates of lanthanide-doped Y2O3 nanoparticles obtained by propellant synthesis

2001 ◽  
Vol 16 (1) ◽  
pp. 146-154 ◽  
Author(s):  
Stefano Polizzi ◽  
Giuliano Fagherazzi ◽  
Marino Battagliarin ◽  
Marco Bettinelli ◽  
Adolfo Speghini
Keyword(s):  
Building Blocks ◽  
Compositional Gradient ◽  
Fractal Aggregates ◽  
Scaling Properties ◽  
X Ray ◽  
Lattice Disorder ◽  
Average Value ◽  
X Ray Scattering ◽  
20 Nm ◽  
Ray Scattering

Y2-xLnxO3 (Ln 4 Ce, Pr, Nd, Eu, Gd, Ho, and Er) powders obtained by propellant synthesis have been characterized using small-angle x-ray scattering, wide-angle x-ray scattering, and transmission and scanning electron microscopy. All the samples showed a very porous, open microstructure with fractal scaling properties. The building blocks of the fractal aggregates are nanocrystallites of lanthanide-doped Y2O3, with variations in the cubic lattice constant proportional to the composition of the solid solution and to the lanthanide ionic radius. The particles had a narrow distribution of sizes with an average value in the 20–50 nm range. They are made of a core of 10–20 nm, consisting of almost perfectly ordered crystals and a “fuzzy” layer, characterized by either a growing lattice disorder or by a compositional gradient. From this dimension, up to at least 200 nm, the particle aggregate is a mass fractal with a fractal dimension, DMf, in the 1.6–2.0 range.

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