Mechanism of Crystalline Self‐Assembly in Aqueous Medium: A Combined Cryo‐TEM/Kinetic Study

Understanding the crystallization of organic molecules is a long‐standing challenge. Herein, a mechanistic study on the self‐assembly of crystalline arrays in aqueous solution is presented. The crystalline arrays are assembled from perylene diimide (PDI) amphiphiles bearing a chiral N‐acetyltyrosine side group connected to the PDI aromatic core. A kinetic study of the crystallization process was performed using circular dichroism spectroscopy combined with time‐resolved cryogenic transmission electron microscopy (cryo‐TEM) imaging of key points along the reaction coordinate, and molecular dynamics simulation of the initial stages of the assembly. The study reveals a complex self‐assembly process starting from the formation of amorphous aggregates that are transformed into crystalline material through a nucleation–growth process. Activation parameters indicate the key role of desolvation along the assembly pathway. The insights from the kinetic study correlate well with the structural data from cryo‐TEM imaging. Overall, the study reveals four stages of crystalline self‐assembly: 1) collapse into amorphous aggregates; 2) nucleation as partial ordering; 3) crystal growth; and 4) fusion of smaller crystalline aggregates into large crystals. These studies indicate that the assembly process proceeds according to a two‐step crystallization model, whereby initially formed amorphous material is reorganized into an ordered system. This process follows Ostwald’s rule of stages, evolving through a series of intermediate phases prior to forming the final structure, thus providing an insight into the crystalline self‐assembly process in aqueous medium.     

Suppression of binary nucleation in amorphous La-Fe-Sb mixtures

The nucleation energy of a series of La(x)Fe(y)Sb(z) modulated elemental reactants was measured as a function of the Fe/Sb ratio over a large composition range while holding the La content constant. The nucleation energy of the ternary compound La(0.5)Fe(4)Sb(12) with the skutterudite crystal structure was found to depend very strongly on the Fe/Sb ratio in the modulated elemental reactant, with a higher nucleation energy as the Fe/Sb ratio is moved away from the 1:3 stoichiometric value. When the results of this study are compared with those from Fe(y)Sb(z) modulated reactants, the addition of lanthanum was found to suppress the nucleation of FeSb(2), thereby broadening the Fe/Sb composition range in which the ternary skutterudite compound La(x)Fe(4)Sb(12) nucleates. This suppression of nucleation of a binary phase on addition of a ternary component to an amorphous intermediate is in agreement with theoretical arguments. The observed suppression of nucleation also provides rational for the observed nucleation of metastable ternary and higher-order compounds from homogeneous amorphous reactants.     

Alignment of Amorphous Iron Oxide Clusters: A Non‐Classical Mechanism for Magnetite Formation

Despite numerous studies on the nucleation and crystallization of iron (oxyhydr)oxides, the roles of species developing during the early stages, especially primary clusters and intermediate amorphous particles, are still poorly understood. Herein, both ligand‐free and ligand‐protected amorphous iron oxide (AIO) clusters (<2 nm) were synthesized as precursors for magnetite formation. Thermal annealing can crystallize the clusters into magnetite particles, and AIO bulk phases with domains of pre‐aligned clusters are found to be direct precursors to crystals, suggesting a non‐classical aggregation‐based pathway that differs from the reported oriented attachment or particle accretion mechanisms.     

Crystal nucleation in an electric field

Nucleation of polar and apolar crystals in an electrostatic field has been analyzed. The analysis is based on the extended nucleation theory which takes into account orientation of amorphous kinetic elements and the resulting crystals. In an electric field free energy of transformation is orientation-dependent which leads to orientation and field effects in thermodynamic (critical crystallization temperature) and kinetic crystallization characteristics (thermal and athermal nucleation rates).     

Multistep crystal nucleation: a kinetic study based on colloidal crystallization

Crystallization via an amorphous precursor, the so-called multistep crystallization (MSC), plays a key role in biomineralization and protein crystallization. MSC has attracted much attention in the past decade, but a quantitative understanding of it has so far not been available. The major challenge is that the kinetics governing the nucleation of crystals occurring in the metastable amorphous precursor remains unclear. In this study, the kinetics of MSC is addressed experimentally. Most importantly, a mathematical method is developed to calculate the local nucleation rate of the crystals in the amorphous precursor, which is not accessible to conventional methods. This local nucleation rate is critical to the understanding of MSC, but it has never been dealt with experimentally because of the difficulties of in situ observation. With the local crystal nucleation rates, the supersaturation for crystallization and the crystal-liquid interfacial free energy in the amorphous precursor are evaluated.     

Application of polyamorphism in water to spontaneous crystallization of emulsified LiCl-H2O solution

Aqueous solutions are widely explained by the hydration or the bound waterfree water notion. Amorphous polymorphism (polyamorphism) in pure water, which is presently under vigorous discussion, may provide a different view over the solutions. Here, I changed pressure, P, temperature, T, and concentration, C, of emulsified LiCl-H2O solutions and studied their freezing by detecting its heat evolution. It was experimentally indicated that the homogeneous nucleation of low-density crystalline ice I (phase Ih or Ic), in pure water and in solutions, connects to the polyamorphic transition of high-density amorphous ice (HDA) to low-density amorphous ice (LDA). Thus, the polyamorphism of water relates to the phase behavior of aqueous solution. In accordance with the recent simulation result, the nucleation was thought to occur in two stages: the appearance of the LDA-like state and the crystallization. Usefulness of the polyamorphic point of view about the solutions was seen.     

Effect of Oxide Coverage on the Growth of Amorphous Al2Pt Phase on an Al Surface

 In the present experiments the high temperature successive deposition (HTSD) of Al and Pt and the half shadowing technique producing wedge shaped area with increasing quantity of deposited Pt are applied for studying the initial stages of solid phase reaction producing amorphous Al₂Pt phase. The nucleation of Al₂Pt phase results in a decoration pattern which could be related to the characteristic local oxide coverage of the Al crystal surface developing by kinetic segregation of oxygen species during the Al film deposition. In the area of larger amount of deposited Pt, where the Al₂Pt phase is continuous Kirkendall voids are present. The samples were investigated in plane by transmission electron microscopy (TEM) and selected area electron diffraction (SAED) and analysed by energy dispersive X-ray spectroscopy (EDX).     

磁场影响聚合物本体结晶动力学的机理分析

在经典的热力学理论基础上,探讨了磁场对聚合物本体结晶过程的成核与生长的影响,建立了相关结晶动力学理论方程.初步认为,磁场产生的＂磁结晶效应＂可能是由于晶相与非晶相之间磁化率差异导致了两相之间磁化能的差异,也可能由于聚合物体系在结晶前会形成一种有序相,减小了体系的熵值,进而改变了结晶过程中的体系自由能,影响其成核与晶体生长,乃至整个结晶动力学方程.利用Matlab软件结合PLLA的各结晶参数值,绘制了结晶自由能与各成核临界参数之间的函数图像.结果表明,在低过冷度下,较小的自由能扰动可能导致较大的晶核临界参数变化.     

The nucleation rate of crystalline ice in amorphous solid water

The kinetics of crystalline ice nucleation and growth in nonporous, molecular beam deposited amorphous solid water (ASW) films are investigated at temperatures near 140 K. We implement an experimental methodology and corresponding model of crystallization kinetics to decouple growth from nucleation and quantify the temperature dependence and absolute rates of both processes. Nucleation rates are found to increase from approximately 3x10(13) m(-3) s(-1) at 134 K to approximately 2x10(17) m(-3) s(-1) at 142 K, corresponding to an Arrhenius activation energy of 168 kJ/mol. Over the same temperature range, the growth velocity increases from approximately 0.4 to approximately 4 A s(-1), also exhibiting Arrhenius behavior with an activation energy of 47 kJ/mol. These nucleation rates are up to ten orders of magnitude larger than in liquid water near 235 K, while growth velocities are approximately 10(9) times smaller. Crystalline ice nucleation kinetics determined in this study differ significantly from those reported previously for porous, background vapor deposited ASW, suggesting the nucleation mechanism is dependent upon film morphology.     

Nucleation of the CO2 hydrate from three-phase contact lines

Using molecular dynamics simulations on the microsecond time scale, we investigate the nucleation and growth mechanisms of CO(2) hydrates in a water/CO(2)/silica three-phase system. Our simulation results indicate that the CO(2) hydrate nucleates near the three-phase contact line rather than at the two-phase interfaces and then grows along the contact line to form an amorphous crystal. In the nucleation stage, the hydroxylated silica surface can be understand as a stabilizer to prolong the lifetime of adsorbed hydrate cages that interact with the silica surface by hydrogen bonding, and the adsorbed cages behave as the nucleation sites for the formation of an amorphous CO(2) hydrate. After nucleation, the nucleus grows along the three-phase contact line and prefers to develop toward the CO(2) phase as a result of the hydrophilic nature of the modified solid surface and the easy availability of CO(2) molecules. During the growth process, the population of sI cages in the formed amorphous crystal is found to increase much faster than that of sII cages, being in agreement with the fact that only the sI hydrate can be formed in nature for CO(2) molecules.     

Composition dependence of the nucleation energy of iron antimonides from modulated elemental reactants.

Modulated elemental reactants containing iron and antimony were found to react at low temperature (T < 200 degrees C) forming either FeSb(2) or FeSb(3) depending on both the layer thicknesses and the overall composition of the initial reactant. For films containing 75% antimony and 25% iron, the metastable compound FeSb(3) was observed to nucleate and grow if the layer thickness was below approximately 35 A. Above this critical thickness for the modulation, annealing led to the formation of FeSb(2). This, combined with low-angle diffraction data, suggests that the initial interdiffusion between iron and antimony layers in an elementally modulated reactant results in the formation of an amorphous reaction intermediate if the layering thickness is less than 35 A. For modulated reactants with composition between 70 and 90 atomic % antimony and below this critical layer thickness, the metastable compound FeSb(3) formed. In more iron-rich modulated reactants FeSb(2) nucleates. The nucleation temperature and the nucleation energy of FeSb(3) were found to be a function of the composition of the amorphous intermediate, while those of FeSb(2) were found to be relatively independent of composition.     

Molecular dynamics studies of the kinetics of phase changes in clusters III: structures, properties, and crystal nucleation of iron nanoparticle Fe331

Molecular dynamics (MD) computer simulations have been carried out to study the structures, properties, and crystal nucleation of iron nanoparticles with 331 Fe atoms or with diameter around 2 nm. Structure information for the nanoparticles was analyzed from the MD simulations. Three crystalline phases and one amorphous phase were obtained by cooling the nanoparticles from their molten droplets at different cooling rates or with different lengths of cooling time periods. Molten droplets froze into three different solid phases and a solid-solid transition from a disordered body-centered cubic (BCC) phase to an ordered BCC phase were observed during the slow cooling and the quenching processes. Properties of nanoparticle Fe₃₃₁, such as melting point, freezing temperature, heat capacity, heat of fusion, heat of crystallization, molar volume, thermal expansion coefficient, and diffusion coefficient, have been estimated. Nucleation rates of crystallization to two solid phases for Fe₃₃₁ at temperatures of 750, 800, and 850 K are presented. Both classical nucleation theory and diffuse interface theory are used to interpret our observed nucleation results. The interfacial free energy and the diffuse interface thickness between the liquid phase and two different solid phases are estimated from these nucleation theories.     

NUCLEATION AND GROWTH ACTIVATION ENERGIES DURING CRYSTALLIZATION OF AMORPHOUS ALLOYS (Ⅰ)——CALCULATION METHOD

A new method is developed for the determination of activation energies for nucleation(E_n) and for growth of nuclei (E_g) during crystallization of amorphous alloys. This methodis based on the crystallization kinetics theory and the experimental results of the variationrelationships of local activation energy E_c(x) and local Avrami exponent n(x) with the crys-tallized volume fraction (x) during crystallization of an amorphous Ni--P alloy. Calculationresults of E_n and E_g in tbe case of crystallization of the amorphous Ni--P alloy by thismethod show that this method is not only simple in the experimental procedures, but alsoaccurate in the quantitative results.     

Free energy of binding of a small molecule to an amorphous polymer in a solvent

Crystallization is a commonly used purification process in industrial practice. It usually begins with heterogeneous nucleation on a foreign surface. The complicated mechanism of heterogeneous nucleation is not well understood, but we hypothesize that a possible correlation between binding affinity to a surface and nucleation enhancement might exist. Amorphous polymers have been used in controlling crystallization. However, to our knowledge, no attempt has been made to calculate the free energy of binding of a small molecule to an amorphous polymer in a solvent, and to characterize the binding sites/conformations of this system at a molecular level. We developed a two-step approach, first using Adsorption Locator to identify probable binding sites and molecular dynamics to screen for the best binding sites and then using the Blue-Moon Ensemble method to compute the free energy of binding. A system of ethylene glycol, polyvinyl alcohol (PVA), and heavy water (D(2)O) was used for validation, since experimental data exists on a related system. Looking at four independently constructed surfaces, we found that ethylene glycol binds to an indentation on the surface or in a hole beneath the surface. We focused on the indentation binding sites because they are easily accessible and do not have large free energy barriers. The closest system for which experimental data on binding energetics exists is ethylene glycol on PVA in aqueous solutions/gels, and the magnitudes of the free energy of binding to the three best indentation binding sites are close to the experimental value, 0.4-3.7 kcal/mol higher. Our approach offers a way to compute the free energy of binding and characterize the binding sites/conformations, and is general enough to apply to other small molecule/amorphous polymer/solvent systems.     

NMR Approach to the kinetics of polymer crystallization. II. Polydimethylsiloxane solutions

The dilution effect on the crystallization kinetics of PDMS/toluene solutions, ranging from a polymer volume fraction of ? = 1.00 (pure PDMS) to ? = 0.32, was studied using ¹H high-power NMR. Spin-spin magnetic response was analyzed into relaxation components, arising from the different phases of the semicrystalline sample, through a spin-echo technique. The intensity and shape of the amorphous component provide relevant information concerning (1) the global crystallization process and (2) the state of hindrance of the amorphous chains induced by the growing crystalline domains. It was shown that, in solutions, the main effect on the crystallization kinetics of changing concentration is to depress the equilibrium melting temperature of the system. However, a radically distinct crystallization rate between the pure and the more concentrated system must be explained in terms of the activation energy for interphase chain transport. Thermodynamic parameters of PDMS crystallites were also deduced from a model. Comparison between the isothermal development of the overall crystallinity and the variation of a characteristic relaxation time of the amorphous PDMS proton response gives an insight into the relative predominance of nucleation or growth rates in the crystallization mechanisms.     

Nucleation and growth of CaCO3 mediated by the egg-white protein ovalbumin: a time-resolved in situ study using small-angle neutron scattering

Mineralization of calcium carbonate in aqueous solutions starting from its initiation was studied by time-resolved small-angle neutron scattering (SANS). SANS revealed that homogeneous crystallization of CaCO 3 involves an initial formation of thin plate-shaped nuclei which subsequently reassemble to 3-dimensional particles, first of fractal and finally of compact structure. The presence of the egg-white protein ovalbumin leads to a different progression of mineralization through several stages; the first step represents amorphous CaCO 3, whereas the other phases are crystalline. The formation and dissolution of the amorphous phase is accompanied by Ca (2+)-mediated unfolding and cross-linking of about 50 protein monomers showing the characteristic scattering of linear chains with a large statistical segment length. The protein complexes act as nucleation centers for the amorphous phase because of their enrichment by Ca (2+) ions. SANS revealed the sequential formation of CaCO 3 starting from the amorphous phase and the subsequent formation of the crystalline polymorphs vaterite and aragonite. This formation from less dense to more dense polymorphs follows the Ostwald-Volmer rule.     

Fe/Dy非晶多层膜晶化反应的热力学及动力学研究

由Miedema半经验公式计算出了Fe Dy二元系自由能图以揭示Fe Dy非晶多层膜的晶化本质。晶化受热力学和动力学两种因素控制 ,Fe,Dy晶态自由能低于初始非晶态 ,提供了晶化的热力学驱动力 ,而形核势垒及临界晶核尺寸控制了晶化反应的相选择 ,因而中等温度退火时先出现Fe晶粒 ,继而Dy晶粒 ,不出现金属间化合物。     

In situ investigation of complex BaSO4 fiber generation in the presence of sodium polyacrylate. 2. Crystallization mechanisms

The formation mechanisms of complex BaSO(4) fiber bundles and cones in the presence of polyacrylate sodium salt via a bioinspired approach at ambient temperature in an aqueous environment are reported. These complex organic-inorganic hybrid structures assemble after heterogeneous nucleation of amorphous precursor particle aggregates on polar surfaces, and the crystallization area can be patterned. In contrast to earlier reports, three different mechanisms based on the oriented attachment of nanoparticles were revealed for the formation of typical fibrous superstructures depending on the supersaturation or on the number of precursor particles. (A) High supersaturation (S > 2): large amorphous aggregates stick to a polar surface, form fiber bundles after mesoscopic transformation and oriented attachment, and then form a narrow tip through polymer interaction. (B) Low supersaturation (S = 1.02-2): only a few fibers nucleate heterogeneously from a single nucleation spot, and amorphous particles stick to existing fibers, which results in the formation of a fiber bundle. (C) Vanishing supersaturation (S = 1-1.02): nucleation of a fiber bundle from a single nucleation spot with self-limiting repetitive growth as a result of the limited amount of building material. These growth processes are supported by time-resolved optical microscopy in solution, TEM, SEM, and DLS.     

Substituent effects on packing entropy and film morphologies in the nucleation of functionalized pentacenes on SiO(2) substrate: Molecular dynamics simulations

The changes in structural ordering, packing entropy, free energy, and film morphologies in the initial nucleation processes of pentacene (Pn), 6, 13-bis(t-butylethynyl) pentacene (t-Bu Pn), and 6, 13-bis(triisopropylsilylethynyl) pentacene (TIPS Pn) on the SiO(2) substrate were investigated, by using the molecular dynamics simulations. During the nucleation, the rod-like Pn molecules tend to diffuse rapidly and have different orientations on the SiO(2) surface. At the low coverage, the t-Bu Pn and TIPS Pn molecules with the branched topological structures almost lie flat on the substrate. On the basis of statistical distribution of various packing configurations of the functionalized Pn pairs, the packing entropy is estimated according to the Boltzmann formula. The packing entropy abruptly decreases in the early stage of deposition. Once the critical nucleus size is reached, the packing entropy converges to a constant value. As the coverage increases, the monolayer films of Pn and its branched derivatives become more ordered. The TIPS Pn with the relatively larger molecular area would occasionally stand on the surface during the nucleation, resulting in the dramatic changes in free energy. In the monolayers, the functionalized Pn molecules are packing more orderly than those in amorphous solids, but less orderly than those in crystals. The degree of order of these monolayers increases as the size of the substituents increases. The understanding of substituent effects on nucleation processes and packing structures is helpful to fabricate organic thin films with well-predefined molecular orientations.