ABSTRACT
This topical review summarizes the theoretical and experimental findings obtained over the last 20â years on the subject of growth-induced polarity formation driven by a Markov chain process. When entering the growing surface of a molecular crystal, an inorganic-organic composite or a natural tissue, the building blocks may undergo 180° orientational disorder. Driven by configurational entropy, faulted orientations can promote the conversion of a growing non-polar seed into an object showing polar domains. Similarly, orientational disorder at the interface may change a polar seed into a two-domain state. Analytical theory and Monte Carlo simulations were used to model polarity formation. Scanning pyroelectric, piezoresponse force and phase-sensitive second-harmonic microscopies are methods for investigating the spatial distribution of polarity. Summarizing results from different types of materials, a general principle is provided for obtaining growth-induced polar domains: a non-zero difference in the probabilities for 180° orientational misalignments of building blocks, together with uni-directional growth, along with Markov chain theory, can produce objects showing polar domains.
ABSTRACT
180° orientational disorder of molecular building blocks can lead to a peculiar spatial distribution of polar properties in molecular crystals. Here we present two examples [4-bromo-4'-nitrobiphenyl (BNBP) and 4-bromo-4'-cyanobiphenyl (BCNBP)] which develop into a bipolar final growth state. This means orientational disorder taking place at the crystal/nutrient interface produces domains of opposite average polarity for as-grown crystals. The spatial inhomogeneous distribution of polarity was investigated by scanning pyroelectric microscopy (SPEM), phase-sensitive second harmonic microscopy (PS-SHM) and selected volume X-ray diffraction (SVXD). As a result, the acceptor groups (NO2 or CN) are predominantly present at crystal surfaces. However, the stochastic process of polarity formation can be influenced by adding a symmetrical biphenyl to a growing system. For this case, Monte Carlo simulations predict an inverted net polarity compared with the growth of pure BNBP and BCNBP. SPEM results clearly demonstrate that 4,4'-dibromobiphenyl (DBBP) can invert the polarity for both crystals. Phenomena reported in this paper belong to the most striking processes seen for molecular crystals, demonstrated by a stochastic process giving rise to symmetry breaking. We encounter here further examples supporting the general thesis that monodomain polar molecular crystals for fundamental reasons cannot exist.
ABSTRACT
The correspondence of the state of alignment of macromolecules in biomimetic materials and natural tissues is demonstrated by investigating a mechanism of electrical polarity formation: An in vitro grown biomimetic FAp/gelatin composite is investigated for its polar properties by second harmonic (SHGM) and scanning pyroelectric microscopy (SPEM). Hexagonal prismatic seed crystals formed in gelatin gels represent a monodomain polar state, due to aligned mineralized gelatin molecules. Later growth stages, showing dumbbell morphologies, develop into a bipolar state because of surface recognition by gelatin functionality: A reversal of the polar alignment of macromolecules, thus, takes place close to that basal plane of the seed. In natural hard tissues (teeth and bone investigated by SPEM) and the biomimetic FAp/gelatin composite, we find a surprising analogy in view of growth-induced states of polarity: The development of polarity in vivo and in vitro can be explained by a Markov-type mechanism of molecular recognition during the attachment of macromolecules.
Subject(s)
Apatites/chemistry , Biomimetic Materials/chemistry , Gelatin/chemistryABSTRACT
Recently, attention has been spent on crystal growth of phosphate compounds in gels for studying the mechanism of in vitro crystallization processes. Here, we present a gel-based approach for the synthesis of barium hydrogen phosphate (BHP) crystals using single and double diffusion techniques in gelatin. The composite crystals were compared with analytical grade BHP powder, single and polycrystalline BHP materials using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), scanning pyroelectric microscopy (SPEM), optical microscopy (OM), thermal gravimetric analysis (TGA) and X-ray diffraction (XRD). FTIR spectra showed surface adsorption of gelatin molecules by using BHP stacked sheets due to CH2 stretching, CH2 bending and amide I vibrations are found in a gelatin content of about 2% determined by dissolution. SEM shows various crystal morphologies of the BHP/gelatin composites forming bundled micro-flakes to irregular bundled needles and spheres different from gel-free crystals. The variety in morphology depends on the ion concentration, pH of gel as well as the method of crystal growth. SPEM investigation of BHP/gelatin aggregates revealed polar domains showing alteration of the polarization. Moreover, BHP/gelatin composite crystals showed a higher thermal stability in comparison with analytical grade BHP or/and BHP single crystals due to strong interactions between gelatin and BHP. The XRD diffraction analysis demonstrated that the single and double diffusion techniques in gelatin led to the formation of orthorhombic BHP. This study demonstrates that gelatin is a useful high molecular weight biomacromolecule for controlling the crystallization of a composite material by producing a variety of morphological forms.
