Size-dependent growth of polymorphs in nanopores and Ostwald's step rule of stages

More than 100 years after Ostwald postulated his step rule of stages, predictive understanding as to early crystallization stages of polymorphic materials is still premature. We studied crystallization of the polymorphic pharmaceutical acetaminophen in nanoporous glasses as a model for early stages of bulk crystallization since the surface energy significantly contributes to the total Gibbs free energy of nanosized crystals in both cases. Systematic studies of transitions between different polymorphs inside nanoporous glasses show that the thermodynamic stability of the polymorphs depends on the crystal size. Accordingly, the transient occurrence of different polymorphs during crystal growth in bulk systems can be related to surface energy contributions to the total Gibbs free energy of the developing crystals. In nanosized early-stage crystals with high surface-to-volume ratios other polymorphs may be stable than in large crystals with low surface-to-volume ratios. Improved control of the crystallization of polymorphic materials by imposing well-defined confinement is a promising strategy to tailor release of polymorphic drugs and to optimize optical, electronic, magnetic and ferroelectric properties of polymorphic materials.     

Physico-chemical characterization of an active pharmaceutical ingredient

The physico-chemical properties and polymorphism of a new active pharmaceutical ingredient entity has been analyzed and the gain of knowledge during the chemical development of the substance is described. Initial crystallization revealed an anhydrous crystal form with good crystallinity and a single, sharp DSC melting peak at 171°C and a straightforward development of this crystal form seemed possible. However, during polymorphism screening, new crystalline forms were detected that were often analyzed as mixtures of crystal forms. The process of characterization and identification of the different crystalline forms and its thermodynamical relationship has been supported by a combination of experimental and computational work including determination of the three-dimensional structures of the crystal forms. The crystal structure of one polymorphic form was solved by single crystal X-ray structure analysis. Unfortunately, Mod B resisted in formation of suitable single crystals, but its structure could be solved by high resolution powder diffraction data analysis using synchrotron radiation. Calculation of the theoretical X-ray powder diffraction pattern from three dimensional crystal coordinates allowed an unambiguous identification of the different crystalline forms. Two polymorphic crystal forms of the API-CG3, named Mod A and Mod B, are enantiotropic whereas Mod B is the most stable polymorph at room temperature up to about 50°C and Mod A at temperatures above 50°C. The mechanism of the solid-solid transition can be explained by analyzing the molecular packing information gained from the single crystal structures. A third crystalline form with the highest melting peak turned out to be not a polymorphic or pseudopolymorphic crystal modification of our API-CG3 but a chemically different substance. This revised version was published online in July 2006 with corrections to the Cover Date.     

Cross-nucleation between ROY polymorphs

Cross-nucleation between polymorphs is a newly discovered phenomenon important for understanding and controlling crystal polymorphism. It contradicts Ostwald's law of stages and other theories of crystallization in polymorphic systems. We studied the phenomenon in the spontaneous and seeded melt crystallization of 5-methyl-2-[(2-nitrophenyl)amino]-3-thiophenecarbonitrile (ROY), currently the most polymorphic system of known structures. We observed extensive and sometimes selective cross-nucleation between ROY polymorphs. Certain polymorphs could not nucleate without the aid of others. The new polymorph was found to be more or less thermodynamically stable than the initial one but to always grow faster than or as fast as the initial one. The temperature and surface characteristics of the seed crystals affected the occurrence of cross-nucleation. Our results show that the pathway of crystallization in polymorphic systems is not determined solely by the initial nucleation, but also by cross-nucleation between polymorphs and the different growth rates of polymorphs. This study identified a new metastable polymorph of ROY, the 10th of the family.     

Crystal engineering: a holistic view

Crystal engineering, the design of molecular solids, is the synthesis of functional solid-state structures from neutral or ionic building blocks, using intermolecular interactions in the design strategy. Hydrogen bonds, coordination bonds, and other less directed interactions define substructural patterns, referred to in the literature as supramolecular synthons and secondary building units. Crystal engineering has considerable overlap with supramolecular chemistry, X-ray crystallography, materials science, and solid-state chemistry and yet it is a distinct discipline in itself. The subject goes beyond the traditional divisions of organic, inorganic, and physical chemistry, and this makes for a very eclectic blend of ideas and techniques. The purpose of this Review is to highlight some current challenges in this rapidly evolving subject. Among the topics discussed are the nature of intermolecular interactions and their role in crystal design, the sometimes diverging perceptions of the geometrical and chemical models for a molecular crystal, the relationship of these models to polymorphism, knowledge-based computational prediction of crystal structures, and efforts at mapping the pathway of the crystallization reaction.     

Polymorphism in spin-crossover systems

The occurrence of spin-crossover (SCO) highly depends on external influences, i.e. temperature, pressure, light irradiation or magnetic field, this electronic switching phenomenon is accompanied by drastic changes in magnetic and optical properties, dielectric constants, colour and structures. Thus, SCO materials are particularly attractive for potential applications in molecular sensing, switching, data storage, display, and other electronic devices at nanometric scale. Polymorphism is widely encountered in the studies of crystallization, phase transition, materials synthesis, biomineralization, and in the manufacture of drugs. Because different crystal forms of the same substance can possess very different properties and behave as different materials, so they are particularly meaningful for investigating SCO phenomena. Studying polymorphism of SCO compounds is therefore important for better understanding the structural factors contributing to spin transition and the structure-function relationship. This critical review is aimed to provide general readers with a comprehensive view of polymorphism in SCO systems. The article is generally structured according to specific metal ions and the dimensionality of compounds in the field. This paper is addressed to readers who are interested in multifunctional materials and tuning magnetic properties through supramolecular chemistry principles (129 references).     

Polymorphie: Fast ein kristallographisches Wintermärchen

A closer look at stories of polymorphic crystals that “appear, ” then “disappear, ” and then ”reappear” again shows that there are no magical mysteries involved. Instead it is the complex interaction between thermodynamics and kinetics that makes the process of crystallization so complex that the experimental results can be almost unbelievable. Clearly the chemists' work is not finished with the pure synthesis, as polymorphic crystals of a new compound have properties which are so different that they might be quite promising one time or undesirable the next. As is true for all fields of chemistry, growing the 'right' crystal form is both a science and an art. Sometimes, though, the mystery that remains is like magic itself.     

Progress in Molecular Nanoarchitectonics and Materials Nanoarchitectonics

Although various synthetic methodologies including organic synthesis, polymer chemistry, and materials science are the main contributors to the production of functional materials, the importance of regulation of nanoscale structures for better performance has become clear with recent science and technology developments. Therefore, a new research paradigm to produce functional material systems from nanoscale units has to be created as an advancement of nanoscale science. This task is assigned to an emerging concept, nanoarchitectonics, which aims to produce functional materials and functional structures from nanoscale unit components. This can be done through combining nanotechnology with the other research fields such as organic chemistry, supramolecular chemistry, materials science, and bio-related science. In this review article, the basic-level of nanoarchitectonics is first presented with atom/molecular-level structure formations and conversions from molecular units to functional materials. Then, two typical application-oriented nanoarchitectonics efforts in energy-oriented applications and bio-related applications are discussed. Finally, future directions of the molecular and materials nanoarchitectonics concepts for advancement of functional nanomaterials are briefly discussed.     

Synthesis of Phosphorylated Indoles

Phosphorylated indoles are widely used not only in pharmaceutical chemistry, but also in the field of fine organic synthesis and materials science. In this regard, the synthesis of such compounds attracts great attention of researchers. This review presents advances in this area over the past 20 years. Particular attention is paid to the catalytic routes of synthesis corresponding to the current trends in organic chemistry.     

The tuning of crystallization behavior of ferroelectric poly(vinylidene fluoride-co-trifluoroethylene)

Poly (vinylidene fluoride-co-trifluoroethylene) [P(VDF-TrFE)] has three crystal forms, including paraelectric α, ferroelectric β, and γ phases. In previous studies, the properties and performances of P(VDF-TrFE) have been the focus of research. However, the formation mechanism and regulation mode of various crystal forms remain unclear. Therefore, it is an important topic for further research to elucidate, summarize, and prospect the polymorphism of P(VDF-TrFE) and regulate the crystal forms. This review systematically summarizes the crystalline structure and phase transition between ferroelectric and paraelectric phase of P(VDF-TrFE) crystals; discusses the influence of annealing, blending and electric field on the crystallinity, selection of polymorphic crystals, and phase transition behavior between them; reviews the effects of annealing, melt-recrystallization, substrate and nanoconfinement on the crystal orientation. Finally, the effects of the crystal structure of P(VDF-TrFE) on its properties are briefly summarized.     

Surface chemistry of CO2 – Adsorption of carbon dioxide on clean surfaces at ultrahigh vacuum

Carbon dioxide chemistry has attracted significant interest in recent years. Although the field is diverse, a current and more comprehensive review of the surface science literature may be of interest for a variety of communities since environmental chemistry, energy technology, materials science, catalysis, and nanocatalysis are certainly affected by gas–surface properties. The review describes surface phenomena and characterization strategies highlighting similarities and differences, instead of providing only a list of system-specific information. The various systems are roughly distinguished as those that clearly form carbonates and those that merely physisorb CO₂ at ultra-high vacuum conditions. Nevertheless, extended sections about specific systems including rarely studied surfaces and unusual materials are included, making this review also useful as a reference.     

The Crystal Chemistry of Copper Oxometalates

Up to three or four years ago oxocuprates were a class of chemical compounds no more remarkable than countless others. Then, as a result of the euphoria surrounding the high-temperature oxide superconductors and the discovery that copper plays an essential role in these materials, there was a world-wide awakening of interest in copper-containing oxide compounds. The number of scientists engaged in the synthesis and structure determination of copper oxometalates has grown from just a few to very many. As superconductivity is inseparably connected with the structure of the solid state, there has been a spontaneous awakening of interest in the role of copper in the crystal chemistry of solid materials, leading to new research projects on this aspect of oxocuprates. Most of the work published so far on the interesting chemistry of this group of compounds has related to individual compounds. New aids in describing complex solid state structures are now available through the development of methods that give three-dimensional displays of crystal structures using computer graphics terminals, as this review illustrates for the example of the oxocuprates.     

Liquid crystal dimers and oligomers

A liquid crystal dimer is composed of molecules containing two mesogenic groups linked via a flexible spacer. Initial interest in these materials stemmed from their ability to act as model compounds for semi-flexible main chain liquid crystal polymers but are now of fundamental interest in their own right because their behaviour is significantly different to that of conventional low molar mass liquid crystals. Recently research has begun to focus also on higher monodisperse oligomers such as trimers and tetramers consisting of molecules containing either three or four mesogenic units, respectively, linked via flexible spacers. In this review the most recent developments in our understanding of structure–property relationships in liquid crystal dimers and higher oligomers is discussed.     

Isomorphism of anhydrous tetrahedral halides and silicon chalcogenides: energy landscape of crystalline BeF2, BeCl2, SiO2, and SiS2

We employ periodic density functional theory calculations to compare the structural chemistry of silicon chalcogenides (silica, silicon sulfide) and anhydrous tetrahedral halides (beryllium fluoride, beryllium chloride). Despite the different formal oxidation states of the elements involved, the divalent halides are known experimentally to form crystal structures similar to known SiX2 frameworks; the rich polymorphic chemistry of SiO2 is however not matched by divalent halides, for which a very limited number of polymorphs are currently known. The calculated energy landscapes yield a quantitative match between the relative polymorphic stability in the SiO2/BeF2 pair, and a semiquantitative match for the SiS2/BeCl2 pair. The experimentally observed polymorphs are found to lie lowest in energy for each composition studied. For the two BeX2 compounds studied, polymorphs not yet synthesized are predicted to lie very low in energy, either slightly above or even in between the energy of the experimentally observed polymorphs. The experimental lack of polymorphism for tetrahedral halide materials thus does not appear to stem from a lack of low-energy polymorphs but more likely is the result of a lack of experimental exploration. Our calculations further indicate that the rich polymorphic chemistry of SiO2 can be potentially matched, if not extended, by BeF2, provided that milder synthetic conditions similar to those employed in zeolite synthesis are developed for BeF2. Finally, our work demonstrates that both classes of materials show the same behavior upon replacement of the 2p anion with the heavier 3p anion from the same group; the thermodynamic preference shifts from structures with large rings to structures with larger fractions of small two and three membered rings.     

X射线晶体学结合电子晶体学在复杂无机晶体结构解析中的应用

自然界中的材料,比如无机材料,有机材料,生物材料等等,均有其独特的物理和化学性质。而材料的性能又与材料的结构息息相关,只有充分了解了材料的结构,才能更加深入的研究材料性质。因此,材料结构的确定在化学、物理、生物等学科中的显得尤为重要。X射线晶体学作为传统的结构解析技术仍然是目前最重要的结构解析手段,但是对于复杂结构,X射线衍射晶体学解析结构也存在一些不足,往往需要其他技术手段相补充才能完成复杂结构的结构解析。电子晶体学虽然起步比X射线晶体学晚,但是,经过近几十年的发展,已经是结构解析领域一个非常重要的手段。本文将主要介绍X射线晶体学结合电子晶体学在复杂无机晶体结构解析中的应用。     

超分子构筑调控合成结构规整的梯形聚合物及其应用研究

综述了"超分子构筑调控的逐步偶联/聚合法",该方法将高分子化学与超分子化学相结合,利用多种类型的超分子弱键协同作用首先构筑预期的梯形超分子结构,再经聚合得到共价键梯形高分子.利用该方法合成了一系列结构规整的氧桥基和有机桥基梯形聚硅氧烷以及碳基梯形聚酯,并利用侧基间π-π叠加作用实现了对聚合物立体构型控制.扼要介绍了梯形聚合物在先进材料方面的应用,例如梯形聚硅氧烷液晶光致取向膜;由梯形聚硅氧烷合成的管状聚硅氧烷在高室温储存期微电子环氧塑封料方面的应用;以及基于梯形聚硅氧烷的拟筛板聚合物在二阶非线性光学材料方面的应用等.     

Effect of copolymerized butylene terephthalate chains on polymorphism and enzymatic degradation of poly(butylene adipate)

The introduction of aromatic butylene terephthalate (BT) units into the backbone chains of aliphatic poly(butylene adipate) (PBA) not only changes the mechanical performance of the resultant P(BA-co-BT) copolymers but also affects their biodegradability. Because of the polymorphism of PBA homopolymer, the copolymerized BT units may also influence the polymorphic crystal structure as well as the biodegradation behavior. In this work, three P(BA-co-BT) copolymers with BT contents as 10, 20, and 25 mol% were chosen to study their polymorphic crystal structure, thermal properties and enzymatic degradation by means of wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC) and gravimetric methods. The results reveal that the P(BA-co-BT) copolymers with BT contents below 25 mol% can form polymorphic crystal structures after melt-crystallization at different temperatures. However, the recrystallization and transformation of polymorphic crystals are strongly affected by the rigid BT units. The enzymatic degradation rates of P(BA-co-BT) copolymers decrease with increasing the BT contents. The influences of the BT units on the polymorphism and enzymatic degradation are discussed in terms of the motion of PBA chains that copolymerized with BT units. It has been concluded from the examination of solid-state microstructure that the influence of the aromatic BT units on the motion of biodegradable PBA chains heavily influences the biodegradability.     

Studying Microstructure in Molecular Crystals With Nanoindentation: Intergrowth Polymorphism in Felodipine

Intergrowth polymorphism refers to the existence of distinct structural domains within a single crystal of a compound. The phenomenon is exhibited by form II of the active pharmaceutical ingredient felodipine, and the associated microstructure is a significant feature of the compound’s structural identity. Employing the technique of nanoindentation on form II reveals a bimodal mechanical response on specific single‐crystal faces, demonstrating distinct properties for two polymorphic forms within the same crystal.     

Molecular Architecture and Function of Polymeric Oriented Systems: Models for the Study of Organization,Surface Recognition,and Dynamics of Biomembranes

The Part and the Whole. The principle of self-organization for the creation of functional units is not an invention of modern natural sciences. It was already a basic idea of the ancient philosophies in Asia and Europe: only the mutuality of the parts creates the whole and its ability to function. Translated into the language of chemistry this means: the self-organization of molecules leads to supramolecular systems and is responsible for their functions. Thermotropic and lyotropic liquid crystals are such functional units, formed by self-organization. As highly oriented systems, they exhibit new properties. The importance of lyotropic liquid crystals for the life sciences has been known for a long time. They are a prerequisite for the development of life and the ability of cells to function. In materials sciences this concept of function through organization led to the development of new liquid-crystalline materials. From the point of view of macromolecular chemistry, this review tries to combine these two different fields and especially hopes to stimulate their interaction and joint treatment. To exemplify this, the molecular architecture of polymeric organized systems will be discussed. Polymeric liquid crystals combine the ability to undergo spontaneous self-organization–typical of liquid-crystalline phases–with the polymer-specific property of stabilizing these ordered states. As new materials, polymeric liquid crystals have already been investigated intensively. As model systems for biomembranes as well as for the simulation of biomembrane processes, they so far have been little discussed. The intention of this review article is to show that polymer science is able to contribute to the simulation of cellular processes such as the stabilization of biomembranes, specific surface recognition, or even the “uncorking” of cells. Polymer science, having an old tradition as an inter-disciplinary field, can no longer restrict itself to common plastics. Attempts to reach new horizons have already begun. The borderland between liquid crystals and cells will certainly play an important role. Basic requirements to work in this frontier area between organic chemistry, membrane biology, life science, and materials science will be the delight in scientific adventures as well as the courage to go ahead. The most important prerequisite will be the willingness to cooperate with disciplines which so far have not really accepted each other. From this point of view, this review does not aim at giving defined answers. It wants instead to encourage the scientific venture: too often we cling to painfully acquired knowledge, fearing adventures.     

Automated preparation method for colloidal crystal arrays of monodisperse and binary colloid mixtures by contact printing with a pintool plotter

Photonic crystals and photonic band gap materials with periodic variation of the dielectric constant in the submicrometer range exhibit unique optical properties such as opalescence, optical stop bands, and photonic band gaps. As such, they represent attractive materials for the active elements in sensor arrays. Colloidal crystals, which are 3D gratings leading to Bragg diffraction, are one potential precursor of such optical materials. They have gained particular interest in many technological areas as a result of their specific properties and ease of fabrication. Although basic techniques for the preparation of regular patterns of colloidal crystals on structured substrates by self-assembly of mesoscopic particles are known, the efficient fabrication of colloidal crystal arrays by simple contact printing has not yet been reported. In this article, we present a spotting technique used to produce a microarray comprising up to 9600 single addressable sensor fields of colloidal crystal structures with dimensions down to 100 mum on a microfabricated substrate in different formats. Both monodisperse colloidal crystals and binary colloidal crystal systems were prepared by contact printing of polystyrene particles in aqueous suspension. The array morphology was characterized by optical light microscopy and scanning electron microscopy, which revealed regularly ordered crystalline structures for both systems. In the case of binary crystals, the influence of the concentration ratio of the large and small particles in the printing suspension on the obtained crystal structure was investigated. The optical properties of the colloidal crystal arrays were characterized by reflection spectroscopy. To examine the stop bands of the colloidal crystal arrays in a high-throughput fashion, an optical setup based on a CCD camera was realized that allowed the simultaneous readout of all of the reflection spectra of several thousand sensor fields per array in parallel. In agreement with Bragg's relation, the investigated arrays exhibited strong opalescence and stop bands in the expected wavelength range, confirming the successful formation of highly ordered colloidal crystals. Furthermore, a narrow distribution of wavelength-dependent stop bands across the sensor array was achieved, demonstrating the capability of producing highly reproducible crystal spots by the contact printing method with a pintool plotter.     

"我"——"三草酸合铁(Ⅲ)酸钾晶体"的生长及影响因素

This article tries to personify potassium ferrioxalate crystal as "I" to describe the formation process and the factors affecting the growth of potassium ferrioxalate crystal. After growing into beautiful green crystals, I dreamed I was participating in the jewelry beauty contest. A serious of wonderful conversations between emerald and I revealed the properties and applications of potassium ferrioxalate crystal. It inspires and guides students to understand the growth of crystals and their properties, and it also stimulates students' interest in studying chemistry.