不同分子质量聚乙二醇对一水草酸钙成核和生长的调控作用

采用扫描电子显微镜(SEM)、X射线衍射(XRD)和原子吸收光谱(AAS)等方法研究了水溶液中分子质量分别为400、4000、6000和12000的聚乙二醇(PEG)对尿结石矿物一水草酸钙(COM)结晶的影响.上述四种PEG均能抑制COM晶体的成核和生长.随着PEG分子质量减小,其与Ca2+离子配位能力逐渐增加,抑制COM生长的能力增强,导致上层清液中可溶性Ca含量增加.随着PEG分子质量减小,或PEG浓度增加,其诱导的COM晶体的{010}晶面增强,{101}减弱.     

Near Supramolecular Isomorphism Involving Homologous Solvents: Pyrimethaminium Terephthalate Methanol Solvate and Pyrimethaminium Terephthalate Ethanol Solvate

Abstract  

Two nearly isostructural pseudopolymorphic forms of pyrimethaminium terephthalate have been synthesized and their supramolecular architectures analyzed. In both the crystals, the protonated pyrimethamine (PMN) cation interacts with the carboxylate anion via N–H···O hydrogen bonds to form the robust R₂²(8) motif. The centrosymmetrically (N–H···N) paired PMN cations are bridged on either sides by interaction of the solvent molecules with the amino groups (N–H···O) of PMN cations. The combination of two R₂²(8) motifs formed between the PMN cations and PMN cation solvent, leads to the formation of the complementary DADA (D = hydrogen bonded donor, A = hydrogen bonded acceptor) array of quadruple hydrogen bonds. The solvent molecule further interacts with the corresponding anion via O–H···O hydrogen bonds. Moreover, both the solvates exhibit several edge to face stacking interactions. They have in common, two C–H···π interactions; one between the symmetry related cations and other between the cation and anion. The molecular packing of the ethanol solvate is further strengthened by C–H···O and C–H···π interaction between the solvent and the ions.     

Semi-Batch Precipitation of Calcium Oxalate Monohydrate

Calcium oxalate monohydrate (COM) formation on the semi-batch precipitation of CaCl₂ and Na₂C₂O₄ solutions in the stoichiometric ratio carried out at pH = 6 and 37 or 70°C, respectively, was studied. When a certain level of supersaturation in the system is reached, individual COM crystals of a rather uniform size are formed. These crystals then grown and form ‘loose’ agglomerates that later develop into compact and spherical particles. The particle size distribution (PSD) rapidly shifts during early stages of precipitation towards larger sizes as a result of crystal growth and agglomeration. Later the PSD reaches a shape and position on the size axis that remain virtually constant with progressing precipitation. COM agglomerates consisting of mainly intergrown crystals are formed by mechanism of primary and secondary agglomeration. The primary agglomeration can constitute an important factor in urolithiasis.     

Etching and Dissolution Mechanism of Cadmium Oxalate Trihydrate Crystals

Dislocation etching and dissolution of gel-grown cadmium oxalate trihydrate crystals are carried out using different etchants. The study revealed the existence of dislocation network in the body of the crystal and shallow dislocation loops in the substructure. Faster dissolution of the crystal at elevated temperatures revealed that the rate of dissolution in the initial part of the dissolution time is much lesser, which increases fast to attain a steady value. This observation is related to the available specific surface area of the crystal.     

Twin structure of Sodium Hydrogen Oxalate Monohydrate

Twin structure of triclinic sodium oxalate monohydrate was determined by means of X-ray techniques. The twin is formed by reticular pseudomerohedry, with [101] as twin axis and (1 01) as contact plane.     

不同结构物质和有机基质对草酸钙晶体生长的促进作用

本文综述了有机大分子、小分子和有机基质对尿石矿物草酸钙(CaOxa)晶体成核、生长和聚集的促进作用.从促进物的分子结构和草酸钙晶体的晶面性质等方面讨论了不同类型促进物的作用机理.最后指出了该领域所面临的问题和将来的发展方向.     

微波辅助草酸盐沉淀法制备四方相钛酸钡纳米粉体

以钛酸四丁酯和硝酸钡为主要原料,采用微波辅助草酸盐沉淀法制备了纯度高、结晶度较好的四方相钛酸钡纳米粉体.分别采用X射线衍射分析(XRD)、扫描电子显微镜(SEM)和透射电子显微镜(TEM)对钛酸钡纳米粉体的结构、粒径及形貌进行表征.结果表明,在钡/钛摩尔比为1,微波温度80 ℃、微波时间30 min,煅烧温度700 ℃,煅烧时间1 h,通过添加表面活性剂OP-10,制备出粒径在50 nm左右且四方度为1.0069的钛酸钡纳米粉体,其中微波合成温度及合成时间对钛酸钡纳米粉体的四方度的影响较大.     

The Crystal and Molecular Structure of the Complex Diaquatetrakis(imidazole)copper(II) Terephthalate Crystal Structure Containing Cu(II) Him and TA

The title compound has been synthesized and its crystals structure determined at room temperature. MW = 536.01, monoclinic, space group C2/c, Z = 4, a = 22.193(5) Å, b = 8.038(2) Å, c = 15.699(4) Å, β = 119.64(2)°. The crystal structure consists of repeated [Cu(Him)₄(H₂O)₂] (Him = imidazole) cations and non-coordinated terephthalato dianions. The copper(II) ion displays an elongated octahedral coordination being linked to the four nitrogen atoms of the four imidazole ligands and to the two oxygen atoms of the two water molecules. The terephthalato dianions are hydrogen bonded to the four water molecules and four imidazole groups.     

The Crystal Structure of Hydrated Barium Copper Oxalate

BaCu(C₂O₄₂.6 H₂O is triclinic, P1 , with a = 6.5405(9), b = 9.202(3), c = 10.939(1) Å, α = 85.46(2), β = 79.22(1), γ = 80.45(2), V = 636.99(1) ų, Z = 2, D₀ = 2.14, D_c = 2.465 g. cm⁻³, R = 0.074, wR = 0.0746 for 2219 significant reflections |F₀|≧ 6.0σF₀. The barium has eleven coordinations and the coordination polyhedra is a capped antiprism. Six water oxygen atoms are coordinated whereas the other five are coming from the oxalate group. In the unit cell the molecules form a polymeric network. One lattice water molecule belongs to the coordinating water. The barium oxygen distances vary from 2.75 Å to 3.15 Å.     

Mechanism of Formation of Cadmium Oxalate Liesegang Rings

Qualitative and semiquantitative study of the Liesegang rings formed by the reaction of oxalic acid and cadmium chloride in the acidic range of pH in silica hydrogel is made. The behaviour of Jablczynski's space constant and Morce-Pierce's time constant at various temperatures, pH and concentration of outer electrolyte is studied. The possible mechanisms for the above observed behaviour are suggested. The deviations from Isemura's general obserations are interprerted by considering two particular aspects, viz., comparatively larger crystals constituting the rings and the irreversibility of inner and outer electrolytes.     

Blends of Poly(Buty1ene Terephthalate) with Thermotropic Liquid Crystalline Polyesters. Morphology and Thermal Behavior

Blends of poly(butylene terephthalate) with liquid crystalline poly (decamethylene 4, 4′-terephthaloyldioxydibenzoate) were studied in all the composition range by optical and electron microscopy and differential calorimetry. The morphology and phase transitions of the blends are markedly influenced by the composition and thermal history. The results suggest the occurrence of miscibility phenomena between the two components in the amorphous phase.     

Magnetic Moment and Susceptibility Measurements of Mixed Rare Earth Oxalate Crystals

The growth of double rare earth oxalate crystals with a general chemical formula AB(C₂O₄)₃ · 10 H₂O (where A and H are Nd, Pr and Sm) is reported. The variation of the magnetic moment of these crystals with an external field is studied and the magnetic susceptibility and the effective magnetic moment are calculated. The observed effective magnetic moment of the crystals are in good agreement with those calculated on theoretical grounds.     

Polymeric AdditiveS' Effect on Crystallization of Calcium Oxalate Scales

Laboratory studies concerned with the effects of polymeric additives on the crystallization of calcium oxalate dihydrate and calcium oxalate monohydrate are described and the results obtained are discussed. These compounds are major components of scales formed in some Australian sugar mills. The studies involved the measurement of crystallization induction periods and rates, in the presence and absence of additives. Crystal morphologies were also examined. A range of experimental conditions were employed, from studies in pure solutions of the lattice ions to those more directly comparable with the mill operation.     

Vickers Micromechanical Indentation Studies of Barium Oxalate Dihydrate Crystals

Vickers microhardness measurements have been carried out on gel grown single crystals of barium oxalate dihydrate. The dependence of hardness on indentation load has been described. Attempts have also been made to understand the cracks developed around the micro indentation. The material chipping off and median vents observed around indentation figures have been discussed. Also explained are the fracture at high indentation load. The average load independent hardness value is 58.27 kg · mm².     

不同形貌二水草酸钙晶体的合成、表征及其对肾上皮细胞的损伤作用

合成了4种不同形貌和尺寸的二水草酸钙(COD)晶体,分别为尺寸20μm的花状、10μm的十字形、2μm的四方双锥形和1μm的棒状COD晶体.采用X射线衍射、傅立叶变换红外光谱、扫描电子显微镜(SEM)和比表面测试仪对上述4个COD晶体的理化性质进行了表征.花状和十字形COD晶体都具有尖锐的棱角;棒状、四方双锥形COD都具有完整的(100)面.随着晶体尺寸的降低和晶体表面正电荷密度高的(100)面比例增大,其Zeta电位绝对值不断减小.不同形貌COD晶体均对非洲绿猴肾上皮细胞(Vero)具有毒性作用,其细胞毒性大小与多因素相关,包括晶体的尺寸、晶面、尖锐程度、比表面积以及Zeta电位等.本研究有助于进一步阐明尿微晶形貌差异影响肾结石形成的分子和细胞机制.     

不同晶相草酸钙晶体的选区电子衍射和X射线衍射比较分析

在卵磷脂-水脂质体中制备了一水草酸钙(COM)、二水草酸钙(COD)和三水草酸钙(COT).并对它们分别进行了透射电镜(TEM)、选区电子衍射分析(SAED)和X射线衍射(XRD)分析.TEM结果表明,COM、COD和COT均为泡状,粒径约80～150nm.将SAED结果与XRD结果对比分析,发现将SAED图谱指标化后所得的衍射数据与XRD的特征峰值基本相符,但在相对强度上存在差别.本实验结果表明,将TEM、SAED和XRD技术联合分析纳米级草酸钙晶体,不但可以观察纳米级草酸钙的形貌,而且能对其晶相、单晶和多晶等进行深入的了解.     

Study of Molecular Structure,Mesomorphism and Their Relation with Molecular Rigidity-Flexibility

Entirely smectogenic novel chalconyl homologue derivatives of thermotropic liquid crystals (LC) have been synthesized with a view to understanding and establishing the effects of molecular structure on liquid crystal properties and the degree of liquid crystallinity. The homologous series consists of 12 (C₁ to C₁₆) homologues with absence of nematogenic character throughout the present series. The textures of smectic phase are fan shaped or batonnet type of smectic-A or of smectic-C. Phase transition temperatures and thermotropic data were determined by an optical polarizing microscope equipped with a heating stage. The smectic–isotropic (Sm-I) phase transition curve and the Cr-Sm transition curve behave in normal manner in the phase diagram. Analytical and spectral data confirm molecular structures of novel homologues. The average thermal stability for smectic is 139.42°C and the mesogenic phase length ranges from 3.5°C to 79.6°C. Mesogenic properties are compared with the structurally similar known series.     

温度变化对草酸钙晶体生长的影响

草酸钙(CaOxa)是泌尿系结石的主要成份,其生长过程受诸多因素的影响.本文研究了温度对CaOxa晶体成核、生长、聚集、晶相、形貌和溶解度等的影响及其机理,对防治泌尿系结石具有启示作用.但高温地区尿石症发病率高的深层次原因还有待进一步研究.     

A New Calcium Oxalate Monohydrate Produced by Thermal Dehydration of Weddellite

A high temperature-Guinier photograph of weddellite power showed at 118 °C a transition to a so far unknown phase which transformed to β-Ca(COO)₂ at 135 °C and during cooling down to whewellite at 103 °C. X-ray diffraction studies on single crystals revealed the new phase to have an orthorhombic symmetry with the lattice constant a = 12.088 Å, b = 10.112 Å, c = 14.634 Å, α = β = γ = 90°. There are very simple orientation relations to weddellite: a₁ (wed) ∥ a (new phase), a₂ (wed) ∥ b (new phase), c (wed) ∥ c (new phase). DTA/TG studies showed that the new phase is a calcium oxalate monohydrate.