Solution-grown chain-folded lamellar single crystals of poly(tetramethylene adipate) (PTMA) were prepared from a dilute solution of 2-methyl-1-propanol by isothermal crystallization. PTMA crystals were hexagonal-shaped and polyethylene decoration of the crystals resulted in a "six cross-sector" surface morphology and showed that the average direction of chain folding is parallel to the crystal growth planes of [110] and [010]. Chain-folded lamellar crystals gave well-resolved electron diffraction diagrams corresponding to all the equatorial reflections of the X-ray fiber diagram obtained from stretched PTMA melt-quenched film (beta structure). The unit cell parameters of the beta structure of PTMA were determined as a = 0.503 nm, b = 0.732 nm and c (fiber axis) = 1.442 nm with an orthorhombic crystal system. The fiber repeat distance is appropriate for an all-trans backbone conformation for the straight stems. The setting angle, with respect to the a axis, is +/-46 degrees for the corner and center chains. Thermal behavior of lamellar crystals has been investigated by means of transmission electron microscopy (TEM) and atomic force microscopy (AFM). The lamellar thickness at the edges of the crystal increased after thermal treatment with taking the molecular chains into recrystallization parts; the holes then opened up at the thickening front of the crystal. The morphological changes of lamellar crystals after enzymatic degradation by Lipase type XIII from Pseudomonas sp. and water-soluble products were characterized by TEM, AFM, gel permeation chromatography, high performance liquid chromatography and fast atom bombardment mass spectrometry. The degradation progressed mainly from the edges of the lamellar crystals without decreasing the molecular weights and the lamellar thicknesses. The central portion of single crystals was often degraded by enzymatic attacks. This result combined with thermal behavior indicates that the loosely chain-packing region exists inside the single crystal, and that molecular chains in this region have higher mobility against thermal and enzymatic treatments. 相似文献
Summary: Solution‐grown lamellar crystals of poly(p‐dioxanone) (PPDX) have been crystallized isothermally from butane‐1,4‐diol at 100 °C. The crystal structure of PPDX has been determined by interpretation of X‐ray fiber diagrams of PPDX fibers and electron diffraction diagrams of lozenge‐shaped chain‐folder lamellar crystals. The unit cell of PPDX is orthorhombic with space group P212121 and parameters: a = 0.970 nm, b = 0.742 nm, and c (chain axis) = 0.682 nm. There are two chains per unit cell, which exist in an antiparallel arrangement.
Transmission electron micrograph of PPDX chain‐folded lamellar crystals obtained by isothermal crystallization and its electron diffraction diagram. 相似文献
The morphology of some amide-hydrazide polymers of the type useful for high-modulus X-500 class fibers has been characterized by transmission electron microscopy of thin films crystallized from dilute solution. Selected area electron diffraction was used to characterize the crystallinity and crystal structure of the thin films and precipitated polymer. The films were cast from concentrated solutions and crystallized by heating the films. The results of these studies revealed several unique features relative to the crystal structure of the all-para polymers. Thin films of the crystallized polymer showed a distinctive crystalline texture—the molecular chains were found to be preferentially oriented parallel to the film plane and randomly oriented about an axis normal to the film plane. Electron diffraction measurements showed equatorial reflection maxima at tilt angles of = 30, ±48, and =59 when the films were tilted on an axis parallel to the film plane. From these results a tentative crystal unit cell and theoretical crystal density were determined: a = 8.5 [Agrave], b = 4.9 Å, c (chain axis) = 29.6 Å, p (density) =1.51 g/cc. The value a/b = 1.735, which is very near 31/2, implies essentially hexagonal packing of the chains. Crystallization from dilute solution revealed lamellar structures resembling “single crystals” in the electron microscope similar to those observed in other crystalline polymers. However, in contrast to these other polymers, these “crystals” are not likely to contain folded chains because of the very rigid nature of the all-para poiyamide-hydrazide. 相似文献
A series of new molecular discs (RDn, here n is the number of carbon atoms between the rod and disc mesogens) was synthesized via the chemical attachment of six cyanobiphenyl calamitic (rod) mesogens (R) linked to the triphenyl discotic (disc) mesogen (D) with a series of six alkyl chain linkages (n = 6-12). In this study, phase structures, transitions, and liquid crystalline (LC) behavior of the RD12 compound with 12 carbon atoms in each alkyl chain linkage between the rod and disc mesogens were investigated. Differential scanning calorimetry, polarized light microscopy, wide-angle X-ray diffraction (WAXD), and selected area electron diffraction (SAED) allowed us to identify three ordered phases below the isotropization temperature: nematic (N) LC and K1 and K2 crystalline phases. On the basis of the structural results obtained via 2D WAXD experiments on oriented samples and SAED experiments on single crystals, the K1 crystalline unit cell was determined to be triclinic with the dimensions of a = 1.36 nm, b = 1.45 nm, c = 2.11 nm, alpha = 85 degrees, beta = 100 degrees, and gamma = 50 degrees. The K2 phase was metastable with respect to the K1 phase. It also possessed a triclinic unit cell with a = 1.40 nm, b = 1.51 nm, c = 1.92 nm, alpha = 87 degrees, beta = 117 degrees, and gamma = 62 degrees. Molecular packing models for the crystalline phases were proposed on the basis of the diffraction results. In the whole range of ordered structures, it was found that RD12 molecular discs are intercalated. Both triphenyl discotic mesogens and cyanobiphenyl calamitic mesogens are completely interdigitated. 相似文献
Single crystals of (NH(4))(4)[(UO(2))(5)(MoO(4))(7)](H(2)O)(5) have been synthesized hydrothermally using (NH(4))(6)Mo(7)O(24), (UO(2))(CH(3)COO)(2).2H(2)O, and H(2)O at 180 degrees C. The phase has been characterized by single-crystal X-ray diffraction using a merohedrally twinned single crystal: it is hexagonal, P6(1), a = 11.4067(5) A, c = 70.659(5) A, V = 7961.9(7) A(3), and Z = 6. The structure is based upon an open framework with composition [(UO(2))(5)(MoO(4))(7)](4-) that is composed of UO(7) pentagonal bipyramids that share vertexes with MoO(4) tetrahedra. The framework has large channels (effective pore size: 4.8 x 4.8 A(2)) parallel to the c axis and a system of smaller channels (effective pore size: 2.5 x 3.6 A(2)) parallel to [100], [110], [010], [110], [110], and [110]. The channels are occupied by NH(4)(+) cations and H(2)O molecules. The topological structure of the uranyl molybdate framework can be described either in terms of fundamental chains of UO(7) pentagonal bipyramids and MoO(4) tetrahedra or in terms of tubular building units parallel to the c axis. 相似文献
The structure of caffeic acid phenethyl ester [2-propenoic acid, 3-(3,4-dihydroxyphenyl)-, 2-phenethyl ester] (I), C17H16O4 x 1/2C6H6, synthesized by base-catalyzed alkylation of caffeic acid salt with beta-bromoethylbenzene in HMPA (hexamethylphosphoramide) and recrystallized from benzene, was confirmed by single crystal X-ray diffraction. The crystals are triclinic, space group P1, Z=2, unit cell dimension a=5.8129 (9) A, b=11.122 (2) A, c=13.226 (2) A, alpha=97.080 (3) degrees, beta=101.467 (3) degrees, gamma=95.405 (3) degrees , V=825.4 (2) A3, Dcalc=1.301 g/cm3, F(000)=342. The packing of the molecule is stabilized by intermolecular O1H...O4 (2.69 A) and O1...HO2 (2.82 A) hydrogen bonds. 相似文献
Understanding the structure-property relationship for organic semiconductors is crucial in rational molecular design and organic thin film process control. Charge carrier transport in organic field-effect transistors predominantly occurs in a few semiconductor layers close to the interface in contact with the dielectric layer, and the transport properties depend sensitively on the precise molecular packing. Therefore, a better understanding of the impact of molecular packing and thin film morphology in the first few monolayers above the dielectric layer on charge transport is needed to improve the transistor performance. In this Article, we show that the detailed molecular packing in thin organic semiconductor films can be solved through a combination of grazing incidence X-ray diffraction (GIXD), near-edge X-ray absorption spectra fine structure (NEXAFS) spectroscopy, energy minimization packing calculations, and structure refinement of the diffraction data. We solve the thin film structure for 2 and 20 nm thick films of tetraceno[2,3-b]thiophene and detect only a single phase for these thicknesses. The GIXD yields accurate unit cell dimensions, while the precise molecular arrangement in the unit cell was found from the energy minimization and structure refinement; the NEXAFS yields a consistent molecular tilt. For the 20 nm film, the unit cell is triclinic with a = 5.96 A, b = 7.71 A, c = 15.16 A, alpha = 97.30 degrees, beta = 95.63 degrees, gamma = 90 degrees; there are two molecules per unit cell with herringbone packing (49-59 degree angle) and tilted about 7 degrees from the substrate normal. The thin film structure is significantly different from the bulk single-crystal structure, indicating the importance of characterizing thin film to correlate with thin film device performance. The results are compared to the corresponding data for the chemically similar and widely used pentacene. Possible effects of the observed thin film structure and morphology on charge carrier mobility are discussed. 相似文献
Morphology control for intense solid‐state phosphorescence of non‐emissive, but potentially emissive crystals of platinum complexes and the mechanistic rationale are described. A series of trans‐bis(salicylaldiminato)platinum(II) complexes bearing linear alkyl chains ( 1 a : n=5; 1 b : n=8; 1 c : n=12; 1 d : n=14; 1 e : n=16; 1 f : n=18) was synthesized and the solid‐state emission properties were examined by using crystals/aggregates prepared under various precipitation conditions. Crystals of 1 e , prepared using “kinetic” conditions including rapid cooling, high concentrations, and poor solvents, emit intensive yellow phosphorescence (λmax=545 nm) under UV irradiation at 298 K with an absolute quantum efficiency of 0.36, whereas all the crystals of 1 a – 1 f prepared using “thermodynamic” conditions including slow cooling, low concentrations, and good solvents were either non‐ or less emissive with Φ298K values of 0.12 ( 1 a ), 0.11 ( 1 b ), 0.10 ( 1 c ), 0.07 ( 1 d ), 0.02 ( 1 e ), and 0.02 ( 1 f ) under the same measurement conditions. The amorphous solid 1 e , prepared by rapid cooling and freeze‐drying, was also non‐emissive (Φ298K=0.02, 0.02). Temperature‐dependent emission spectra showed that the kinetic crystals of 1 e exhibit high heat‐resistance towards emission decay with increasing temperature, whereas the amorphous solid 1 e is entirely heat‐quenchable. This is a rare example of the change from a non‐emissive crystal into a highly emissive crystal by morphology control through crystal engineering. Emission spectra and powder X‐ray diffraction (XRD) patterns of the emissive, kinetic crystals of 1 e are clearly distinct from those of the less emissive, thermodynamic crystals of 1 a – 1 f . Single‐crystal XRD unequivocally establishes that the thermodynamic crystals of 1 d have a multilayered lamellar structure supported by highly regulated, consecutive π‐stacking interactions between imine moieties, whereas the kinetic crystals of 1 e have a face‐to‐edge lamellar structure with less stacking. These results lead to the conclusion that 1) morphology control of long‐chained complexes exclusively generates a metastable herringbone‐based lamellar packing motif that exhibits intense emission and high heat‐resistance, while 2) a thermodynamically stable, highly regulated, consecutive stacking motif is unfavorable for solid‐state emission. 相似文献
A 3D infinitely extended structural rare earth coordination compound with a formula of K3{[Sm(H2O)7]2Na[α-SiW11O39Sm(H2O)4]2}·14H2O has been synthesized by reaction of Sm2O3, HClO4, NaOH with α-K8SiW11O39·nH2O, and characterized by IR,UV spectra, ICP, TG-DTA, cyclic voltammetry, variable-temperature magnetic susceptibility and X-ray single-crystal diffraction.X-ray single-crystal diffraction indicates that the title compound crystallizes in a triclinic lattice, Pī space group, with a=1.2462(3) nm, b=1.2652(3) nm,c=1.8420(4) nm,α=87.45(3)°,β=79.91(3)°,γ=82.57(3)°,Z=1, R1=0.0778,wR2=0.1610.Structural analysis reveals that Sm3+(1) coordination cation has incorporated into the vacant site of [α-SiW11O39]8- entity,forming the [α-SiW11O39Sm(H2O)4]5- subunit.The two adjacent [α-SiW11O39Sm(H2O)4]5- subunits are combined with each other through two Sm(1)-O-W bridges accompanying the formation of dimmer structural unit [α-SiW11O39Sm(H2O)4]210- of the title compound.The neighboring dimmer structural units [α-SiW11O39Sm(H2O)4]210- are linked to form the 1D chainlike structure by means of two Sm3+(2) and a Na+(1) coordination cations.The K+(1) cations connect the 1D packing chains constructing the 2D netlike structure, and adjacent netlike layers are also grafted by K+(2) cations to build the novel 3D infinitely extended structure.The result of TG-DTA curves manifests that the decomposition temperature of the title polyanionic framework is 554℃.The cyclic voltammetry measurements show that the title polyanion has the two-step redox processes in aqueous solution with pH=3.1.Variable temperature magnetic susceptibility indicates the title compound obeys the Cruie-Weiss Law in the higher temperature range from 110 to 300 K, while in the lower temperature range from 2 to 110 K the comparatively strong antiferromagnetism interactions can be observed. 相似文献
The thermal phase transition and self-assembly behaviors in water of the crystalline lamellar films prepared from unsymmetrical bolaamphiphiles, N-(2-aminoethyl)-N'-(beta-d-glucopyranosyl)-alkanediamide [1(n), n = 12, 14, 16, 17, 18, and 20], have been studied using differential scanning calorimetry, polarized light microscopy, variable-temperature (VT) X-ray diffraction (XRD), and VT-IR spectroscopy. The behavior allowed us to classify the bolaamphiphiles into two categories: short chain 1(n) (n = 12, 14, 16, and 17) and long chain 1(n) (n = 18 and 20). On heating, the films of the long chain 1(n) exhibited polymorphism of two crystal phases (Cr1 and Cr2) and one thermotropic mesophase (smectic). These phases proved to consist of unsymmetrical monolayer lipid membranes (MLMs), in which the molecules packed in a parallel fashion. On the other hand, the films of the short chain 1(n) gave a single crystal phase (Cr1) consisting of symmetrical MLMs with antiparallel molecular packing. Scanning transmission electron microscopy and atomic force microscopy revealed that the long chain 1(n) self-assembles in alkaline aqueous solutions to form nanotubes with 110-120 nm outer diameters, while the short chain 1(n) produces nanotapes with 80-250 nm widths. XRD and IR measurements revealed that the nanotubes consist of unsymmetrical MLMs, while the nanotapes consist of symmetrical MLMs. The molecular packing of the initial solid phase was essentially maintained even in the self-assemblies in water. The self-assembly process in water allowed the symmetrical MLM films of the short chain 1(n) to convert into the symmetrical MLM nanotapes. Similarly, the unsymmetrical MLM films of the long chain 1(n) were converted into the unsymmetrical MLM nanotubes. 相似文献
The crystallite orientation and lamellar deformation produced by hot-rolling in polyethylene have been investigated. In the lightly rolled stage, the [110]* axis of polyethylene crystals orientates in the plane perpendicular to the rolling direction and the c axis becomes aligned with the rolling direction. In the heavily rolled stage the a, b, and c axes coincide with the macroscopic directions in the sample. These orientational changes are interpreted in terms of a slip mechanism. Small-angle x-ray scattering (SAXS) investigations of hot-rolled polyethylene show the following. (1) There are two kinds of lamellar structures; one in which inclined lamellae give a four-point diagram in the SAXS photograph and another in which lamellar normals are oriented around the rolling direction even at the lightly rolled stage. The latter structure is attributed to the mechanism of unfolding and recrystallization. (2) The chain-fold length in the original structure remains unchanged in the lamellae up to a roll ratio of four although the apparent long period decreases. This is explained by inclination of polymer chains in the lamellae. Further rolling aligns the polymer chains with the rolling direction and the fold length decreases. 相似文献
The structure of regenerated cellulose is shown by x-ray diffraction to be comprised of an array of antiparallel chain molecules. The determination was based on the intensity data from rayon fibers and utilized rigid-body least-squares refinement techniques. The unit cell is monoclinic with space group P2(1) and dimensions a = 8.01 A, b = 9.04 A, c = 10.36 A (fiber axis), and gamma = 117.1 degrees. Models containing chains with the same sense (parallel) or alternating sense (antiparallel) were refined against the intensity data. The only acceptable model contains antiparallel chains. The -CH2OH groups of the corner chain are oriented near to the gt position while those of the center chain are near to the tg position. Both chains possess an O3-H-O5' intramolecular hydrogen bond, and the center chain also has an O2'-H-O6 intramolecular bond. Intermolecular hydrogen bonding occurs along the 020 planes (o6-h-o2 bonds for the corner chains and O6-H-O3 bonds for the center chains) and also along the 110 planes with a hydrogen bond between the O2-H of the corner chain and the O2' of the center chain. This center-corner chain hydrogen bonding is a major difference between the native and regenerated structures and may account for the stability of the latter form. 相似文献
UraniumIV sulfate in an aqueous solution and the solid state has been investigated with extended X-ray absorption fine structure (EXAFS) and X-ray diffraction (XRD). The coordination polyhedron comprises monodentate sulfate, bidentate sulfate, and water molecules. The coordination modes of sulfate in solution have been determined from the U-S distances with EXAFS. The U-S distance of 3.67 +/- 0.02 A indicates monodentate sulfate, and the U-S distance of 3.08 +/- 0.02 A indicates bidentate coordination. The obtained sulfur coordination numbers of a solution with a [SO42-]/[U4+] ratio of 40 suggest species with compositions of [U(SO4,bid)2(SO4,mon)2 x nH2O]4- and [U(SO4,bid)3 (SO4,mon)2 x mH2O]6-. Charge-compensating countercations or ion pairing with Na+ and NH4+ could not be detected with EXAFS. One of the solution species, [U(SO4)5H2O]6-, has been conserved in a crystal. The corresponding crystal structure of Na1.5(NH4)4.5[U(SO4)5 x H2O] x H2O [space group P1, a = 9.4995(16) A, b = 9.8903(16) A, c = 12.744(2) A, alpha = 93.669(2) degrees, beta = 103.846(2) degrees, gamma = 109.339(2) degrees] has been determined by single-crystal XRD. Two monomeric uraniumIV sulfate complexes and three sodium units are linked in alternating rows and form a one-dimensional ribbon structure parallel to the a axis. 相似文献