Calcium oxalate crystals in tomato and tobacco plants: morphology and in vitro interactions of crystal-associated macromolecules

Plants form calcium oxalate crystals with unique morphologies under well-controlled conditions. We studied the morphology of single calcium oxalate monohydrate (whewellite) crystals extracted from tomato and tobacco leaves. These crystals have a pseudotetrahedral shape. We identified the (101), (101) or (102), (110), and (hk0) faces as stable faces. The morphology is chiral with unique handedness. We also show that calcium oxalate monohydrate crystals isolated from tomato, tobacco, and bougainvillea leaves contain macromolecules rich in Gly, Glx, and Ser. Crystal-associated macromolecules extracted from tomato and tobacco influence the morphology of calcium oxalate monohydrate crystals grown in vitro, promoting preferential development of the [120] faces. Furthermore, crystal-associated macromolecules from tobacco promote nucleation of calcium oxalate monohydrate crystals, whereas model polypeptides do not have any significant effect on nucleation. These results imply an active role of the crystal-associated macromolecules in the formation of pseudotetrahedral shapes in vitro, and these properties may in part be responsible for the unique chiral morphology of the natural pyramidal-shaped crystals.     

The Story Behind the Link between Molecular Chirality and Crystal Shape

Here we describe the story behind the link between molecular chirality and macroscopic phenomena, the latter being a probe for the direct assignment of absolute configuration of chiral molecules. First, a brief tour of the history of molecular stereochemistry, starting with the classic experiment reported by Pasteur in 1848 on the separation of enantiomorphous crystals of a salt of tartaric acid, and his conclusion that the molecules of life are chiral of single-handedness. With time, this study raised, inter alia, two fundamental questions: the absolute configuration of chiral molecules and how a molecule of given configuration shapes the enantiomorphous morphology of its crystal. As for the first question, following the beginning of crystal structure determination by X-ray diffraction in 1912, it took almost 40 years before Bijvoet assigned molecular chirality through the esoteric method involving anomalous X-ray scattering. We have been able to address and link both questions through ‘everyday concepts of left and right’ (in the words of Jack Dunitz) by the use of ‘tailor-made’ auxiliaries. By such means, it proved possible to reveal, through morphology, etch patterns, epitaxy and symmetry reduction of both chiral and, paradoxically, centrosymmetric crystals, the basic chiral symmetry of the molecules of life, the α-amino acids and sugars.     

Investigation of an Unusual Crystal Habit of Hydrochlorothiazide Reveals Large Polar Enantiopure Domains and a Possible Crystal Nucleation Mechanism

The observation of an unusual crystal habit in the common diuretic drug hydrochlorothiazide (HCT), and identification of its subtle conformational chirality, has stimulated a detailed investigation of its crystalline forms. Enantiomeric conformers of HCT resolve into an unusual structure of conjoined enantiomorphic twin crystals comprising enantiopure domains of opposite chirality. The purity of the domains and the chiral molecular conformation are confirmed by spatially revolved synchrotron micro‐XRD experiments and neutron diffraction, respectively. Macroscopic inversion twin symmetry observed between the crystal wings suggests a pseudoracemic structure that is not a solid solution or a layered crystal structure, but an unusual structural variant of conglomerates and racemic twins. Computed interaction energies for molecular pairs in the racemic and enantiopure polymorphs of HCT, and the observation of large opposing unit‐cell dipole moments for the enantiopure domains in these twin crystals, suggest a plausible crystal nucleation mechanism for this unusual crystal habit.     

How Crystal Symmetry Dictates Non-Local Vibrational Circular Dichroism in the Solid State

Solid-State Vibrational Circular Dichroism (VCD) can be used to determine the absolute structure of chiral crystals, but its interpretation remains a challenge in modern spectroscopy. In this work, we investigate the effect of a twofold screw axis on the solid-state VCD spectrum in a combined experimental and theoretical analysis of P2₁ crystals of (S)-(+)-1-indanol. Even though the space group is achiral, a single proper symmetry operation has an important impact on the VCD spectrum, which reflects the supramolecular chirality of the crystal. Distinguishing between contributions originating from molecular chirality and from chiral crystal packing, we find that while IR absorption hardly depends on the symmetry of the space group, the situation is different for VCD, where completely new non-local patterns emerge. Understanding the two underlying mechanisms, namely gauge transport and direct coupling, will help to use VCD to distinguish polymorphic forms.     

Mirror Symmetry Breaking by Chirality Synchronisation in Liquids and Liquid Crystals of Achiral Molecules

Spontaneous mirror symmetry breaking is an efficient way to obtain homogeneously chiral agents, pharmaceutical ingredients and materials. It is also in the focus of the discussion around the emergence of uniform chirality in biological systems. Tremendous progress has been made by symmetry breaking during crystallisation from supercooled melts or supersaturates solutions and by self‐assembly on solid surfaces and in other highly ordered structures. However, recent observations of spontaneous mirror symmetry breaking in liquids and liquid crystals indicate that it is not limited to the well‐ordered solid state. Herein, progress in the understanding of a new dynamic mode of symmetry breaking, based on chirality synchronisation of transiently chiral molecules in isotropic liquids and in bicontinuous cubic, columnar, smectic and nematic liquid crystalline phases is discussed. This process leads to spontaneous deracemisation in the liquid state under thermodynamic control, giving rise to long‐term stable symmetry‐broken fluids, even at high temperatures. These fluids form conglomerates that are capable of extraordinary strong chirality amplification, eventually leading to homochirality and providing a new view on the discussion of emergence of uniform chirality in prebiotic systems.     

二水草酸钙的形成及其对尿路结石的防治

二水草酸钙(COD)是泌尿系结石的主要成分之一,其成核、生长和聚集过程与尿石的形成密切相关。本文结合我们近年来的工作,综述了生物膜及其模拟膜对COD的调控作用,尿大分子、焦磷酸盐、多磷酸盐、柠檬酸、酒石酸及表面活性剂等尿小分子的诱导作用,过饱和度、化学计量条件、pH值、离子强度、温度等体系参数对COD形成的影响;讨论了COD的形貌、晶面电荷及其与细胞膜粘附的研究进展。从临床上预防和治疗草酸钙结石的角度,综述了有利于COD形成的因素。     

Simulation of calcium oxalate stone in vitro

Urolithiasis constitutes a serious health problem that affects a significant section of mankind. Between 3% and 14% of the population, depending on the geographical region, suffer from this illness[1]. For example, the incidence of urolithiasis in Florida in the United States of America was 15.7 in 100000 people and increased to 20.8 in 1996. Urolithiasis remains a major medical prob-lem in China, especially in Guangdong Province. A survey in 1997 in Shenzhen City, the most southern city i…     

The separation of racemic crystals into enantiomers by chiral block copolymers

A series of chiral double hydrophilic block copolymers (DHBCs) was synthesized and employed as additives in the crystallization of calcium tartrate tetrahydrate (CaT). We found that appropriate polymers can slow down the formation of the thermodynamically most stable racemic crystals as well as the formation of one of the pure enantiomeric crystals so that chiral separation by crystallization occurs even when racemic crystals can be formed. In addition, the presence of DHBCs results in major modifications of crystal morphology, creating unusual morphologies of higher complexity. Our study demonstrates the potential application of chiral DHBCs in the control of chirality throughout crystallization, in particular for racemic crystal systems, and also shows that enantiomeric excess of one enantiomer can be maximized by the kinetic control of crystallization.     

Simulation of calcium oxalate stone <Emphasis Type="Italic">in vitro</Emphasis>

Crystallization of calcium oxalate is studied mainly in the diluted healthy urine using scanning electron microscopy (SEM), and is compared with the crystallization in the diluted pathological urine. It suggests that the average sizes of calcium oxalate crystals are not in direct proportion to the concentrations of Ca²⁺ and Ox^2- ions. Only in the concentration range of 0.60-0.90 mmol/L can larger size of CaOx crystals appear. When the concentrations of Ca²⁺ and Ox^2- ions are 1.20, 0.80, 0.60, 0.30 and 0.15 mmol/L in the healthy urine, the average sizes of calcium oxalate crystallites are 9.5 X 6.5, 20.0 X 13.5 and 15.0 jj,m X 10.0 jj,m, respectively, for the former three samples after 6 d crystallization. No crystal appears even after 30 d crystallization for the samples of concentrations of 0.30 and 0.15 mmol/L due to their low supersaturations. The results theoretically explain why the probability of stone forming is clinically not in direct proportion to the concentrations of Ca²⁺ and Ox^2- ions. Laser scattering technology also confirms this point. The reason why healthy human has no risk of urinary stone but stone-formers have is that there are more urinary macromolecules in healthy human urines than that in stone-forming urines. These macromolecules may control the transformation in CaOx crystal structure from monohydrate cal-cium oxalate (COM) to dihydrate calcium oxalate (COD). COD has a weaker affinity for renal tubule cell membranes than COM. No remarkable effect of the crystallization time is observed on the crystal morphology of CaOx. All the crystals are obtuse hexagon. However, the sizes and the number of CaOx crystals can be affected by the crystallization time. In the early stage of crystalli-zation (1-6 d), the sizes of CaOx crystals increase and the number of crystal particles changes little as increasing the crystallization time due to growth control. In the middle and late stages (6-30 d), the number of crystals increases markedly while the growth rate changes little due to the nucleation control.     

LB膜诱导下草酸钙晶体的生物矿化研究

草酸钙（CaC２O４）结石是生物体内异常矿化形成的产物，是泌尿系结石的主要组成部分犤１犦。它形成于泌尿系统中尿路表皮细胞上犤２犦。磷脂的Langmuir－Blodgett（LB）膜是生物细胞膜的简化模拟体系犤３犦。用磷脂LB膜作为模板来研究CaC２O４晶体的形成过程，比在水溶液中更能接近CaC２O４结石在生物体内细胞膜表面形成的真实情况，将有助于对尿路结石的形成及防治的研究犤４犦。尿大分子硫酸软骨素A（C４S）存在于尿液中，但不存在于CaC２O４结石中。在结石病人尿液中C４S的含量明显低于正常人尿液中的含量，因此推测其在体内…     

Vibrational Circular Dichroism Spectroscopy of Chiral Molecular Crystals: Insights from Theory

Chirality is a curious phenomenon that appears in various forms. While the concept of molecular (RS-)chirality is ubiquitous in chemistry, there are also more intricate forms of structural chirality. One of them is the enantiomorphism of crystals, especially molecular crystals, that describes the lack of mirror symmetry in the unit cell. Its relation to molecular chirality is not obvious, but still an open question, which can be addressed with chiroptical tools. Vibrational circular dichroism (VCD) denotes chiral infrared (IR) spectroscopy that is susceptible to both, the molecular as well as the intermolecular space by means of vibrational transitions. When carried out in the solid state, VCD delivers a very rich set of non-local contributions that are determined by crystal packing and collective motion. Since its discovery in the 1970s, VCD has become the method of choice for the determination of absolute configurations, but its applicability reaches beyond towards the study of different crystal forms and polymorphism. This brief review summarises the theoretical concepts of crystal chirality and how computations of solid-state VCD can shed light into the intimate connection of chiral structure and vibrational optical activity.     

In Situ Controlled Construction of a Hierarchical Supramolecular Chiral Liquid‐Crystalline Polymer Assembly

Hierarchical supramolecular chiral liquid‐crystalline (LC) polymer assemblies are challenging to construct in situ in a controlled manner. Now, polymerization‐induced chiral self‐assembly (PICSA) is reported. Hierarchical supramolecular chiral azobenzene‐containing block copolymer (Azo‐BCP) assemblies were constructed with π–π stacking interactions occurring in the layered structure of Azo smectic phases. The evolution of chirality from terminal alkyl chain to Azo mesogen building blocks and further induction of supramolecular chirality in LC BCP assemblies during PICSA is achieved. Morphologies such as spheres, worms, helical fibers, lamellae, and vesicles were observed. The morphological transition had a crucial effect on the chiral expression of Azo‐BCP assemblies. The supramolecular chirality of Azo‐BCP assemblies destroyed by 365 nm UV irradiation can be recovered by heating–cooling treatment; this dynamic reversible achiral–chiral switching can be repeated at least five times.     

Helical polyacetylene—Origins and synthesis

We present the origins and synthesis of helical polyacetylene (H‐PA) by focusing on its peculiar spiral morphology. Interfacial polymerization of acetylene was carried out in an asymmetric reaction field consisting of chiral nematic liquid crystal (N*‐LC) and Ziegler–Natta catalyst. As the N*‐LC is composed of nematic liquid crystal and a chiral compound such as a binaphthyl derivative with either the R‐ or S‐configuration, the screw directions of the polyacetylene chain and fibril bundle—and even the spiral morphology—are rigorously controlled by the chirality of the selected compound. Interestingly, the screw directions of the fibril and the bundle in H‐PA were found to be opposite to that of N*‐LC. It is worthwhile to emphasize that the hierarchical spiral morphology involving the primary to higher order structure is generated in a synthetic polymer such as polyacetylene by using N*‐LC as an asymmetric polymerization solvent. © 2008 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 8: 395–406; 2008: Published online in Wiley InterScience ( www.interscience.wiley.com ) DOI 10.1002/tcr.20163     

Light‐Directed Dynamic Chirality Inversion in Functional Self‐Organized Helical Superstructures

Helical superstructures are widely observed in nature, in synthetic polymers, and in supramolecular assemblies. Controlling the chirality (the handedness) of dynamic helical superstructures of molecular and macromolecular systems by external stimuli is a challenging task, but is of great fundamental significance with appealing morphology‐dependent applications. Light‐driven chirality inversion in self‐organized helical superstructures (i.e. cholesteric, chiral nematic liquid crystals) is currently in the limelight because inversion of the handedness alters the chirality of the circularly polarized light that they selectively reflect, which has wide potential for application. Here we discuss the recent developments toward inversion of the handedness of cholesteric liquid crystals enabled by photoisomerizable chiral molecular switches or motors. Different classes of chiral photoresponsive dopants (guests) capable of conferring light‐driven reversible chirality inversion of helical superstructures fabricated from different nematic hosts are discussed. Rational molecular designs of chiral molecular switches toward endowing handedness inversion to the induced helical superstructures of cholesteric liquid crystals are highlighted. This Review is concluded by throwing light on the challenges and opportunities in this emerging frontier, and it is expected to provide useful guidelines toward the development of self‐organized soft materials with stimuli‐directed chirality inversion capability and multifunctional host–guest systems.     

The role of vinyl sulfonic acid homopolymer in calcium oxalate crystallization

In this study, the effect of water soluble homopolymer of vinylsulfonic acid on spontaneous crystallization of calcium oxalate (CaOx) was investigated. CaOx crystals exhibiting different shapes and phase structures were produced in the presence of polymer. While the crystal growth of calcium oxalate was inhibited by homopolymer, the morphology of calcium oxalate transformed from monohydrate to dihydrate. Inhibition of calcium oxalate crystallization was provided by adsorption of homopolymer onto the active growth sites of crystals on account of the charge and hydrophilic effects. Polyelectrolyte effects were interpreted in terms of the adsorption of inhibitors onto the active growth sites on the crystal surface.     

海藻异枝麒麟菜多糖抑制尿石盐草酸钙晶体生长的研究

采用扫描电子显微镜(SEM)、 红外光谱(FTIR)和X射线衍射(XRD)方法研究了从海藻异枝麒麟菜中提取的硫酸多糖(ESPS)对草酸钙(CaOxa)晶体生长的影响. 结果表明, 添加ESPS能抑制一水草酸钙(COM)的生长, 同时诱导二水草酸钙(COD)晶体的形成. 随着ESPS的质量浓度从0增加到0.03和0.50 mg/mL, COD的质量分数从0分别增加到10%和55%; COM的(1 01)晶面加强, (020)晶面减弱直至消失, 并从三维晶体转变为棱角圆顿的四角形片状晶体; COM和COD的尺寸均明显变小. 这些结果表明, ESPS是抑制CaOxa结石形成的一种潜在药物.     

Partial ordering of tripivaloylmethane at 110 K

Tripivaloylmethane [systematic name: 4‐(2,2‐dimethylpropanoyl)‐2,2,6,6‐tetramethylheptane‐3,5‐dione], C₁₆H₂₈O₃, is known to crystallize at room temperature in the space group R3m with three molecules in the unit cell. The molecules are conformationally chiral and pack so that each molecular site is occupied with equal probability by the two enantiomers. Upon cooling to 110 K, the structure partially orders; two molecules in the unit cell order into two different conformations of opposite chirality, while the third remains disordered. The symmetry of the resulting crystal is P3, with each of the molecules lying about a different threefold rotation axis. This paper describes an unusual case of order–disorder phase transition in which the structure partially orders by changes of molecular conformation in the single crystals. Such behaviour is of interest in the study of phase transitions and molecular motion in the solid state.     

Inhibition of the Crystal Growth and Aggregation of Calcium Oxalate by Algae Sulfated Polysaccharide In-vitro

Kidney stone disease causes substantial suffering and occasional renal failure. The content of calcium oxalate (CaOxa) is up to 70-80% in the stones1,2. However, the mechanism of the formation of urinary stones is not yet clearly understood and the questi…     

沙苑子提取液对不同体系中草酸钙晶体生长影响的研究

通过与水、氯化钠、正常人尿液体系的比较,重点研究了结石患者尿液体系中加入中药沙苑子提取液对草酸钙晶体生长的的影响,利用SEM,FTIR和XRD等测试手段对所得晶体进行表征。结果发现:在结石患者尿液体系中形成的草酸钙晶体为一水草酸钙(COM)晶体,而在这4种体系中加入沙苑子提取液后,只形成二水草酸钙(COD)晶体,表明沙苑子提取液能抑制COM晶体生长,并且随着沙苑子提取液浓度增大,抑制作用增强。沙苑子抑制草酸钙晶体生长的可能机理进行了探讨。     

L-半胱氨酸自组装膜诱导草酸钙结晶研究

在CaCl2.H2O和Na2C2O4配制的过饱和溶液中,利用L-半胱氨酸(L-Cys)在金片上形成的自组装膜为模板,研究了草酸钙(CaOxa)在自组装膜上的结晶行为,并探讨了溶液pH对CaOxa晶体组成、晶型及其形貌的影响。采用X射线衍射(XRD)和扫描电子显微镜(SEM)等技术对CaOxa晶体的结构和形貌进行了表征。实验结果表明:当溶液pH=3.0时,溶液中可以形成一水草酸钙(CaC2O4.H2O,COM)和二水草酸钙(CaC2O4.2H2O,COD)晶体,而在同样pH条件下,在L-Cys自组装膜上只形成COD晶体,表明自组装单层对CaOxa晶体的成核和生长有重要影响。通过改变溶液的pH,在自组装单层上可以得到不同晶型和不同形状的CaOxa晶体。当pH=3.0时得到四方块状的COD晶体,而pH=5.0和pH=7.0时分别得到六边形和拉长六边形的COM晶体。