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Gelation with Small Molecules: from Formation Mechanism to NanostructureArchitecture

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Low Molecular Mass Gelator

Part of the book series: Topics in Current Chemistry ((TOPCURRCHEM,volume 256))

Abstract

The mechanism of fiber and fiber network formation of small molecular gelling agents is treated on the basis of a generic heterogeneous nucleation model. The formation of a crystallite fiber network can take place via the so-called crystallographic mismatch branching. At very low supersaturations, unbranched fibers form predominantly. As supersaturation increases, small-angle crystallographic mismatch branching occurs at the side face of growth fibers. At very high supersaturations, the so-called wide-angle crystallographic mismatch branching becomes kinetically favorable. Both give rise to the formation of fiber networks, but of different types. Controlling the branching of the nanofibers of small molecular gelatins allows us to achieve the micro/nanostructure architecture of networks having the desired rheological properties. In this regard, the engineering of supramolecular functional materials can be achieved by constructing and manipulating the micro/nanostructure in terms of a “branching creator”, or by tuning processing conditions.

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Abbreviations

a :

Activity

C :

Concentration

D f :

Fractal or Hausdorff~Besicovitch dimension of a pattern

d :

Diameter of an object

DIOP:

Di-(2-ethylhexyl phthalate) (C8H17COO)2 (C6H4)

EVACP:

Ethylene/vinyl acetate copolymer

f(m):

Interfacial correlation function

G * :

Complex modulus

G′:

Storage modulus

G′′:

Loss modulus

GP-1:

N-lauroyl-l-glutamic acid di-n-butylamide

ΔG :

Gibbs free-energy barrier

h :

Height of step of crystal surface

Δh m :

Enthalpy of melting per molecule

ISA:

Isostearyl alcohol

L-DHL:

Lanosta-8,24-dien-3β-ol:24,25-dihydrolanosterol = 56:44

J :

Nucleation rate

k :

Boltzmann constant

m :

Interfacial matching parameter

N :

Number of particles or segments

N g :

Number of crystals per volume

P :

Pressure

r c :

Radius of curvature of critical nucleus

R :

Radius of gyration of a pattern

R g :

Growth rate of fiber along the axial direction

SA-CMB:

Small-angle crystallographic mismatch branching

SEM:

Scanning electron microscopy

T :

Temperature

t s :

Nucleation induction time

t :

Time

WA-CMB:

Wide-angle crystallographic mismatch branching

νg :

Growth rate of bulk crystals

X :

Crystallinity of a system

φ:

Volume fraction of crystal materials

γ:

Interfacial free energy

γstep :

Step free energy of crystal surface

μ:

Chemical potential

η:

Viscosity

θ:

Contact angle

Ω:

Volume per structural unit

τ:

Induction time for the nucleation of new fibers on the host fibers

σ:

Supersaturation

ω:

Angular frequency

ξ:

Branching distance

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Authors and Affiliations

  1. Department of Physics, Faculty of Science, National University of Singapore, 2 Science Drive 3, 117542, Singapore, Singapore

    Xiang Y. Liu

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  1. Xiang Y. Liu
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Liu, X.Y. (2005). Gelation with Small Molecules: from Formation Mechanism to NanostructureArchitecture. In: Low Molecular Mass Gelator. Topics in Current Chemistry, vol 256. Springer, Berlin, Heidelberg. https://doi.org/10.1007/b107170

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