Macromolecular crystal growth as revealed by atomic force microscopy

McPherson, Alexander; Kuznetsov, Yurii G.; Malkin, Alexander J.; Plomp, Marco

doi:10.1016/s1047-8477(03)00036-4

Cited by 49 publications

(43 citation statements)

References 52 publications

(64 reference statements)

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“…The characteristic interstep distance in these macrosteps [30-60 nm (39)] is significantly smaller than the mean cluster diameter (250 ± 50 nm). Incorporation of a solid amorphous cluster or a microcrystal on a sloped surface would not lead to a perfect merging of both phases (40), which contradicts numerous observations made in this work; (ii) on many occasions, we detected microcrystals that sedimented on a single macrocrystal (Fig. 3C) and time-lapse imaging showed that these microcrystals are not a source of large multilayer stacks, hence no successful fusion was made with both lattices.…”

Section: Resultscontrasting

confidence: 84%

Role of clusters in nonclassical nucleation and growth of protein crystals

Sleutel

Driessche

2014

Proc. Natl. Acad. Sci. U.S.A.

165

204

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The development of multistep nucleation theory has spurred on experimentalists to find intermediate metastable states that are relevant to the solidification pathway of the molecule under interest. A great deal of studies focused on characterizing the so-called "precritical clusters" that may arise in the precipitation process. However, in macromolecular systems, the role that these clusters might play in the nucleation process and in the second stage of the precipitation process, i.e., growth, remains to a great extent unknown. Therefore, using biological macromolecules as a model system, we have studied the mesoscopic intermediate, the solid end state, and the relationship that exists between them. We present experimental evidence that these clusters are liquidlike and stable with respect to the parent liquid and metastable compared with the emerging crystalline phase. The presence of these clusters in the bulk liquid is associated with a nonclassical mechanism of crystal growth and can trigger a self-purifying cascade of impurity-poisoned crystal surfaces. These observations demonstrate that there exists a nontrivial connection between the growth of the macroscopic crystalline phase and the mesoscopic intermediate which should not be ignored. On the other hand, our experimental data also show that clusters existing in protein solutions can significantly increase the nucleation rate and therefore play a relevant role in the nucleation process.prenucleation clusters | phase transition | self-purification T he process of crystallization is generally considered to occur in two consecutive but very different stages: nucleation and growth. The first stage was already studied more than two centuries ago by Gibbs, who considered the nucleation of water droplets from a supersaturated vapor through the formation of globulae. He was the first to develop a thermodynamic formalism of nucleation by considering the generation of nuclei of a liquid phase as a density fluctuation of the parent phase (1, 2). Since then, Gibbs' nucleation theory has been extended to the nucleation of solid phases from solution and gaseous phases from which the current paradigm (based on the capillary approximation) for nucleation emerged, i.e., the classical nucleation theory ]. There is, however, an increasing body of evidence that shows that CNT can fail drastically when used in cases where the implicit and explicit assumptions of CNT are poorly justified (for a full dissection of the limitations, see refs. 9-11). An obvious situation where CNT will have limited applicability is in cases where the old and the new phases differ by at least two order parameters, e.g., density and structure (12).Recent theoretical, computational, and experimental efforts have demonstrated that densification and local increase in crystallinity need not occur simultaneously (13)(14)(15)(16)(17)(18)(19)(20). These results have inspired the development of a new approach that considers nucleation from solution as a multistep process attributing key roles to metastabl...

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Section: Resultscontrasting

confidence: 84%

Role of clusters in nonclassical nucleation and growth of protein crystals

Sleutel

Driessche

2014

Proc. Natl. Acad. Sci. U.S.A.

165

204

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“…[Tangential growth as a whole was examined by Burton, Cabrera, and Frank (12); Frank's contribution was the analysis of screw dislocations (14)]. These 2 processes produce characteristic target and spiral patterns seen at the molecular scale in solid crystals (15). These same patterns are visible in the conspicuous features of the surface of nacre at the mesoscale in Fig.…”

Section: Liquid-crystal Layer Growth Model Of Nacrementioning

confidence: 96%

Spiral and target patterns in bivalve nacre manifest a natural excitable medium from layer growth of a biological liquid crystal

Cartwright

Checa

Escribano

et al. 2009

Proc. Natl. Acad. Sci. U.S.A.

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Nacre is an exquisitely structured biocomposite of the calcium carbonate mineral aragonite with small amounts of proteins and the polysaccharide chitin. For many years, it has been the subject of research, not just because of its beauty, but also to discover how nature can produce such a superior product with excellent mechanical properties from such relatively weak raw materials. Four decades ago, Wada [Wada K (1966) Spiral growth of nacre. Nature 211:1427] proposed that the spiral patterns in nacre could be explained by using the theory Frank [Frank F (1949) The influence of dislocations on crystal growth. Discuss Faraday Soc 5:48 -54] had put forward of the growth of crystals by means of screw dislocations. Frank's mechanism of crystal growth has been amply confirmed by experimental observations of screw dislocations in crystals, but it is a growth mechanism for a single crystal, with growth fronts of molecules. However, the growth fronts composed of many tablets of crystalline aragonite visible in micrographs of nacre are not a molecular-scale but a mesoscale phenomenon, so it has not been evident how the Frank mechanism might be of relevance. Here, we demonstrate that nacre growth is organized around a liquid-crystal core of chitin crystallites, a skeleton that the other components of nacre subsequently flesh out in a process of hierarchical self-assembly. We establish that spiral and target patterns can arise in a liquid crystal formed layer by layer through the Burton-Cabrera-Frank [Burton W, Cabrera N, Frank F (1951) The growth of crystals and the equilibrium structure of their surfaces. Philos Trans R Soc London Ser A 243:299 -358] dynamics, and furthermore that this layer growth mechanism is an instance of an important class of physical systems termed excitable media. Artificial liquid crystals grown in this way may have many technological applications.biomineralization ͉ chitin ͉ interlamellar membranes ͉ mollusc T he splendor of a pearl extends even to under a microscope; with magnification, one can see that the nacreous surfaces of bivalve mollusks-clams, mussels, oysters, scallops, and so onare made up of a striking arrangement of spiral, target, and labyrinthine patterns (1); see Fig. 1. Nacre, or mother of pearl, is the iridescent material that forms an inner layer of the shells of numerous species of mollusks as well as the pearls that many of those same species produce. The structure of nacre is often likened to a brick wall, and indeed, it is composed of bricks of aragonite tablets (Ϸ95%) and mortar of organic so-called interlamellar membranes (polysaccharide and protein, Ϸ5%), but it is a brick wall built in a peculiar fashion, because first, the mortar is put in place, and then the bricks grow within it. (See Fig. 2 for a sketch of bivalve molluscan anatomy and nacre structure.) From an examination of the extrapallial space of the bivalve mollusk, the narrow liquid-filled cavity between the soft tissues and the shell of the organism, it is seen that the first visible feature in nacre growth ...

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“…[11][12][13][14] In situ AFM studies of differing resolution have been reported for a number of MOFs, [15][16][17][18][19] revealing valuable information concerning their crystal growth and the growth of nanoporous materials.…”

Section: Introductionmentioning

confidence: 99%

Crystal growth of MOF-5 using secondary building units studied by in situ atomic force microscopy

et al. 2014

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(2014) 'Crystal growth of MOF-5 using secondary building units studied by in situ atomic force microscopy. ', CrystEngComm., 16 (42). pp. 9834-9841. Further information on publisher's website:https://doi.org/10.1039/C4CE01710BPublisher's copyright statement:Additional information: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Crystal growth of the metal-organic framework, MOF-5, using basic zinc benzoate, [Zn 4 O(O 2 CC 6 H 5 ) 6 ], was studied in real time using atomic force microscopy. The twodimensional nuclei involved in layer growth were found to form by a two-step process whereby 1,4-benzenedicarboxylate units first attach to the MOF-5 surface followed by addition of a layer of Zn species and connecting 1,4-benzenedicarboxylate units. 6 ]-containing growth solutions were found to influence the relative growth rates along different crystallographic directions and to lead to a faster nucleation rate under certain conditions when compared to growth solutions containing simpler zinc salts. This suggests a degree of remnant association of the zinc species derived from the [Zn 4 O(O 2 CC 6 H 5 ) 6 ] cluster during crystal growth under these conditions. IntroductionPorous metal-organic frameworks (MOFs) are formed from the connection of metal ions and organic linkers to provide an enormous number of different structures of varying pore dimension, geometry and functionality that are finding potential use in a diverse array of new and traditional applications. [1][2][3][4] Considerable effort has been expended to optimise the synthesis of these materials with regards to numerous factors including: yield, crystal size, morphological control, the rate of product formation and the synthesis temperature. One such approach to the synthesis of MOFs is the so called "controlled secondary building unit (SBU) approach" (CSA) introduced by Serre et al. 5 The rationale behind the development of this approach was that MOF syntheses could be speeded up if the metal components added to the reaction solution were already preassembled to resemble the SBUs of the final crystalline MOF. This method has succeeded in decreasing reaction times and temperatures for several MOFs,[5][6][7] in addition to proving to be very useful in the synthesis of nanoparticles, 8 thin films, 9 and producing MOF homologues with new metal content. 6One of the questions arising from the CSA methodology is whether the SBU remains intact during synthesis. If it does then this would suggest that formation of the MOF can occur via a simple ligand substitution ...

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Macromolecular crystal growth as revealed by atomic force microscopy

Cited by 49 publications

References 52 publications

Role of clusters in nonclassical nucleation and growth of protein crystals

Role of clusters in nonclassical nucleation and growth of protein crystals

Spiral and target patterns in bivalve nacre manifest a natural excitable medium from layer growth of a biological liquid crystal

Crystal growth of MOF-5 using secondary building units studied by in situ atomic force microscopy

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