Crystallization of Tyrian Purple (6,6'-Dibromoindigo) Thin Films: The Impact of Substrate Surface Modifications.

The pigment 6,6'-dibromoindigo (Tyrian purple) shows strong intermolecular hydrogen bonds and the film formation is, therefore, expected to be influenced by the polar character of the substrate surface. Thin films of Tyrian purple were prepared by physical vapor deposition on a variety of substrates with different surface energies: from highly polar silicon dioxide surfaces to hydrophobic polymer surfaces. The crystallographic properties were investigated by X-ray diffraction techniques such as X-ray reflectivity and grazing incidence X-ray diffraction. In all cases, crystallites with "standing" molecules relative to the substrate surface were observed independently of the substrate surface energy. In the case of polymer surfaces, additional crystallites are formed containing "lying" molecules with their aromatic planes parallel to the substrate surface. Small differences in the crystallographic lattice constants were observed as a function of substrate surface energy, the corresponding small changes in the molecular packing are explained by a variation of the hydrogen bond geometries. This work reveals that despite the limited influence of the surface energy on the molecular orientation, the crystalline packing of Tyrian purple within thin films is altered and slightly different structures form.

Correlation between two- and three-dimensional crystallographic lattices for epitaxial analysis. I. Theory.

The epitaxial growth of molecular crystals at single-crystalline surfaces is often strongly related to the first monolayer at the substrate surface. The present work presents a theoretical approach to compare three-dimensional lattices of epitaxially grown crystals with two-dimensional lattices of the molecules formed within the first monolayer. Real-space and reciprocal-space representations are considered. Depending on the crystallographic orientation relative to the substrate surface, proper linear combinations of the lattice vectors of the three-dimensional unit cell result in a rhomboid in the xy plane, representing a two-dimensional projection. Mathematical expressions are derived which provide a relationship between the six lattice parameters of the three-dimensional case and the three parameters obtained for the two-dimensional surface unit cell. It is found that rotational symmetries of the monolayers are reflected by the epitaxial order. Positive and negative orientations of the crystallographic contact planes are correlated with the mirror symmetry of the surface unit cells, and the corresponding mathematical expressions are derived. The method is exemplarily applied to data obtained in previous grazing-incidence X-ray diffraction (GIXD) measurements with sample rotation on thin films of the conjugated molecules 3,4;9,10-perylenetetracarboxylic dianhydride (PTCDA), 6,13-pentacenequinone (P2O), 1,2;8,9-dibenzopentacene (trans-DBPen) and dicyanovinyl-quaterthiophene (DCV4T-Et2) grown by physical vapor deposition on Ag(111) and Cu(111) single crystals. This work introduces the possibility to study three-dimensional crystal growth nucleated by an ordered monolayer by combining two different experimental techniques, GIXD and low-energy electron diffraction, which has been implemented in the second part of this work.

Impact of sample misalignment on grazing incidence x-ray diffraction patterns and the resulting unit cell determination.

Grazing incidence x-ray diffraction (GIXD) is a frequently used tool for the crystallographic characterization of thin films in terms of polymorph identification and determination of the crystallographic lattice parameters. Even full structure solutions are possible. To obtain highly accurate diffraction patterns, the thin film sample has to be aligned carefully with the center of the goniometer, which allows a defined incidence of the primary x-ray beam relative to the sample surface. This work studies the effect of misalignment of a thin film sample on the acquired diffraction pattern. Three potential types of misalignments are considered: the deviation of the sample surface from the center of the goniometer, an error in the incidence angle of the primary beam, and an inclination of the goniometer rotation axis from the normal of the substrate surface. The consequence of these types of sample misalignments is the shift of diffraction peaks toward specific directions in reciprocal space. Mathematical equations are given that relate the error in positions of Bragg peaks for each type of sample misalignment. Experiments with intentionally misaligned samples confirm the given formulas. In a subsequent step, the errors in the peak positions are translated to systematic errors in the estimation of the unit cell parameters. Depending on the type of misalignment, some alignment errors can be reduced or even corrected; in particular, azimuthal sample rotations prove to be advantageous in these cases. The results in this work improve the quality of GIXD measurements, in general, enabling deeper analysis like the full structure solution from the GIXD pattern on everyday basis.

Correlation between two- and three-dimensional crystallographic lattices for epitaxial analysis. II. Experimental results.

While the crystal structure of the polymorph phase can be studied in three dimensions conveniently by X-ray methods like grazing-incidence X-ray diffraction (GIXD), the first monolayer is only accessible by surface-sensitive methods that allow the determination of a two-dimensional lattice. Here, GIXD measurements with sample rotation are compared with distortion-corrected low-energy electron diffraction (LEED) experiments on conjugated molecules: 3,4;9,10-perylenetetracarboxylic dianhydride (PTCDA), 6,13-pentacenequinone (P2O), 1,2;8,9-dibenzopentacene (trans-DBPen) and dicyanovinyl-quaterthiophene (DCV4T-Et2) grown by physical vapor deposition on Ag(111) and Cu(111) single crystals. For these molecular crystals, which exhibit different crystallographic lattices and crystal orientations as well as epitaxial properties, the geometric parameters of the three-dimensional lattice are compared with the corresponding geometry of the first monolayer. A comparison of the monolayer lattice from LEED investigations with the multilayer lattices determined by rotated GIXD experiments reveals a correlation between the first monolayer and the epitaxial growth of three-dimensional crystals together with lattice distortions and re-alignment of molecules. The selected examples show three possible scenarios of crystal growth on top of an ordered monolayer: (i) growth of a single polymorph, (ii) growth of three different polymorphs; in both cases the first monolayer serves as template. In the third case (iii) strong lattice distortion and distinct molecular re-alignments from the monolayer to epitaxially grown crystals are observed. This is the second part of our work concerning the correlation between two- and three-dimensional crystallographic lattices for epitaxial analysis. In the first part, the theoretical basis has been derived which provides a mathematical relationship between the six lattice parameters of the three-dimensional case and the three parameters obtained for the two-dimensional surface unit cell, together with their orientation to the single-crystalline substrate. In this work, a combined experimental approach of GIXD and LEED is introduced which can be used to investigate the effect of the epitaxial monolayer on the structural properties of molecular crystals grown on top.

GIDInd: an automated indexing software for grazing-incidence X-ray diffraction data.

Grazing-incidence X-ray diffraction (GIXD) is a widely used technique for the crystallographic characterization of thin films. The identification of a specific phase or the discovery of an unknown polymorph always requires indexing of the associated diffraction pattern. However, despite the importance of this procedure, only a few approaches have been developed so far. Recently, an advanced mathematical framework for indexing of these specific diffraction patterns has been developed. Here, the successful implementation of this framework in the form of an automated indexing software, named GIDInd, is introduced. GIDInd is based on the assumption of a triclinic unit cell with six lattice constants and a distinct contact plane parallel to the substrate surface. Two approaches are chosen: (i) using only diffraction peaks of the GIXD pattern and (ii) combining the GIXD pattern with a specular diffraction peak. In the first approach the six unknown lattice parameters have to be determined by a single fitting procedure, while in the second approach two successive fitting procedures are used with three unknown parameters each. The output unit cells are reduced cells according to approved crystallographic conventions. Unit-cell solutions are additionally numerically optimized. The computational toolkit is compiled in the form of a MATLAB executable and presented within a user-friendly graphical user interface. The program is demonstrated by application on two independent examples of thin organic films.

Searching for New Polymorphs by Epitaxial Growth.

The formation of unknown polymorphs due to the crystallization at a substrate surface is frequently observed. This phenomenon is much less studied for epitaxially grown molecular crystals since the unambiguous proof of a new polymorph is a challenging task. The existence of multiple epitaxial alignments of the crystallites together with the simultaneous presence of different polymorphs does not allow simple phase identification. We present grazing incidence X-ray diffraction studies on conjugated molecules like perylenetetracarboxylic dianhydride (PTCDA), pentacene, dibenzopentacene (trans-DBPen), and dicyanovinylquater-thiophene (DCV4T-Et2) grown by physical vapor deposition on single crystalline surfaces like Ag(111), Cu(111), and graphene. A new method for indexing the observed Bragg peaks allows the determination of the crystallographic unit cells so that the type of crystallographic phase can be clearly identified. This approach even works when several polymorphs are simultaneously present within a single sample as shown for DCV4T-Et2 on Ag(111). Additionally, epitaxial relationships between the epitaxially grown crystallites and the single crystalline surfaces are determined. In a subsequent step, the experimental data are used for the crystal structure solution of an unknown polymorph, as shown for the example trans-DBPen grown on Cu(111).

Phase Transition toward a Thermodynamically Less Stable Phase: Cross-Nucleation due to Thin Film Growth of a Benzothieno-benzothiophene Derivative.

The molecule 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene is an organic semiconductor, with outstanding properties in terms of molecular packing and its use in organic electronics. The asymmetric shape of the molecule causes a double layer crystal structure at room temperature. In this work we report its thin film growth by physical vapor deposition starting from the monolayer regime up to thick films. The films are studied in terms of their morphology, crystallographic properties, and thermal stability by atomic force microscopy and X-ray diffraction methods. It is found that the bulk molecular packing of the bilayer is formed at the initial thin film growth stage. After a thickness of one double layer, a transition into a new polymorph is observed which is of metastable character. The new phase represents a single layer phase; the crystal structure could be solved by a combination of X-ray diffraction and molecular dynamics simulations. The observed thin film growth is outstanding in terms of surface crystallization: the formation of a metastable phase is not associated with the initial thin film growth, since the first growth stage represents rather the bulk crystal structure of this molecule. Its formation is associated with cross-nucleation of one polymorph by another, which explains why a metastable phase can be formed on top of a thermodynamically more stable phase.

An efficient method for indexing grazing-incidence X-ray diffraction data of epitaxially grown thin films.

Crystal structure identification of thin organic films entails a number of technical and methodological challenges. In particular, if molecular crystals are epitaxially grown on single-crystalline substrates a complex scenario of multiple preferred orientations of the adsorbate, several symmetry-related in-plane alignments and the occurrence of unknown polymorphs is frequently observed. In theory, the parameters of the reduced unit cell and its orientation can simply be obtained from the matrix of three linearly independent reciprocal-space vectors. However, if the sample exhibits unit cells in various orientations and/or with different lattice parameters, it is necessary to assign all experimentally obtained reflections to their associated individual origin. In the present work, an effective algorithm is described to accomplish this task in order to determine the unit-cell parameters of complex systems comprising different orientations and polymorphs. This method is applied to a polycrystalline thin film of the conjugated organic material 6,13-pentacenequinone (PQ) epitaxially grown on an Ag(111) surface. All reciprocal vectors can be allocated to unit cells of the same lattice constants but grown in various orientations [sixfold rotational symmetry for the contact planes (102) and (102)]. The as-determined unit cell is identical to that reported in a previous study determined for a fibre-textured PQ film. Preliminary results further indicate that the algorithm is especially effective in analysing epitaxially grown crystallites not only for various orientations, but also if different polymorphs are present in the film.

Indexing grazing-incidence X-ray diffraction patterns of thin films: lattices of higher symmetry.

Grazing-incidence X-ray diffraction studies on organic thin films are often performed on systems showing fibre-textured growth. However, indexing their experimental diffraction patterns is generally challenging, especially if low-symmetry lattices are involved. Recently, analytical mathematical expressions for indexing experimental diffraction patterns of triclinic lattices were provided. In the present work, the corresponding formalism for crystal lattices of higher symmetry is given and procedures for applying these equations for indexing experimental data are described. Two examples are presented to demonstrate the feasibility of the indexing method. For layered crystals of the prototypical organic semiconductors di-indeno-perylene and (ortho-di-fluoro)-sexi-phenyl, as grown on highly oriented pyrolytic graphite, their yet unknown unit-cell parameters are determined and their crystallographic lattices are identified as monoclinic and orthorhombic, respectively.

MRI in paediatric hypoxic-ischemic disease, metabolic disorders and malformations-a review.

MRI has become the most important modality in paediatric neuroimaging. It provides an excellent anatomical overview with good spatial and temporal resolution, allows investigations of the blood vessels, and - using technologies such as diffusion-weighted imaging and magnetic resonance spectroscopy - it allows quick and exact differentiation of ischemic, hypoxic, inflammatory, oncologic, traumatic and metabolic diseases. This review presents an overview of brain MRI in infants and children with suspected hypoxic-ischemic disease, metabolic disorders or (vascular) malformations, illustrating these issues by some MRI findings in selected important conditions and discussing some major clinical and pathophysiological aspects important for imaging.

Indexing of grazing-incidence X-ray diffraction patterns: the case of fibre-textured thin films.

Crystal structure solutions from thin films are often performed by grazing-incidence X-ray diffraction (GIXD) experiments. In particular, on isotropic substrates the thin film crystallites grow in a fibre texture showing a well defined crystallographic plane oriented parallel to the substrate surface with random in-plane order of the microcrystallites forming the film. In the present work, analytical mathematical expressions are derived for indexing experimental diffraction patterns, a highly challenging task which hitherto mainly relied on trial-and-error approaches. The six lattice constants a, b, c, α, ß and γ of the crystallographic unit cell are thereby determined, as well as the rotation parameters due to the unknown preferred orientation of the crystals with respect to the substrate surface. The mathematical analysis exploits a combination of GIXD data and information acquired by the specular X-ray diffraction. The presence of a sole specular diffraction peak series reveals fibre-textured growth with a crystallographic plane parallel to the substrate, which allows establishment of the Miller indices u, v and w as the rotation parameters. Mathematical expressions are derived which reduce the system of unknown parameters from the three- to the two-dimensional space. Thus, in the first part of the indexing routine, the integers u and v as well as the Laue indices h and k of the experimentally observed diffraction peaks are assigned by systematically varying the integer variables, and by calculating the three lattice parameters a, b and γ. Because of the symmetry of the derived equations, determining the missing parameters then becomes feasible: (i) w of the surface parallel plane, (ii) the Laue indices l of the diffraction peak and (iii) analogously the lattice constants c, α and ß. In a subsequent step, the reduced unit-cell geometry can be identified. Finally, the methodology is demonstrated by application to an example, indexing the diffraction pattern of a thin film of the organic semiconductor pentacenequinone grown on the (0001) surface of highly oriented pyrolytic graphite. The preferred orientation of the crystallites, the lattice constants of the triclinic unit cell and finally, by molecular modelling, the full crystal structure solution of the as-yet-unknown polymorph of pentacenequinone are determined.

Surface-Induced Phase of Tyrian Purple (6,6'-Dibromoindigo): Thin Film Formation and Stability.

The appearance of surface-induced phases of molecular crystals is a frequently observed phenomenon in organic electronics. However, despite their fundamental importance, the origin of such phases is not yet fully resolved. The organic molecule 6,6'-dibromoindigo (Tyrian purple) forms two polymorphs within thin films. At growth temperatures of 150 °C, the well-known bulk structure forms, while at a substrate temperature of 50 °C, a surface-induced phase is observed instead. In the present work, the crystal structure of the surface-induced polymorph is solved by a combined experimental and theoretical approach using grazing incidence X-ray diffraction and molecular dynamics simulations. A comparison of both phases reveals that π-π stacking and hydrogen bonds are common motifs for the intermolecular packing. In-situ temperature studies reveal a phase transition from the surface-induced phase to the bulk phase at a temperature of 210 °C; the irreversibility of the transition indicates that the surface-induced phase is metastable. The crystallization behavior is investigated ex-situ starting from the sub-monolayer regime up to a nominal thickness of 9 nm using two different silicon oxide surfaces; island formation is observed together with a slight variation of the crystal structure. This work shows that surface-induced phases not only appear for compounds with weak, isotropic van der Waals bonds, but also for molecules exhibiting strong and highly directional hydrogen bonds.

Prevertebral tendinitis: how to avoid unnecessary surgical interventions.

OBJECTIVES/HYPOTHESIS: Prevertebral tendinitis is an inflammatory process that affects the cervicothoracic prevertebral muscles. Because of its clinical presentation and imaging features in computed tomography scans, prevertebral tendinitis can easily be mistaken for deep cervical abscess formation. Totally different therapy regimens require clinical and diagnostic pathways for sufficient differentiation between those two pathologic entities. STUDY DESIGN: Case series with comparison. METHODS: In 10 patients with prevertebral tendinitis, we evaluated the symptoms, laboratory reports, and radiological imaging findings. We compared these data to 65 patients with a deep cervical abscess formation. The basic radiologic imaging procedure was contrast-enhanced computed tomography. For detection of prevertebral tendinitis, we performed magnetic resonance imaging with diffusion-weighted images and calculated the apparent diffusion coefficient map. RESULTS: Patients with prevertebral tendinitis complained of severe neck pain, globus sensation, and neck stiffness. Diffusion-weighted images showed a typical benign prevertebral effusion. Computed tomography scans showed amorphous calcifications in the tendon of the prevertebral muscles. The C-reactive protein values were slightly increased in patients with prevertebral tendinitis, and white blood cell count remained normal. In comparison to patients with deep cervical abscess formation, the C-reactive protein and white blood cell count was significantly lower (P < .05) in the prevertebral tendinitis cases. CONCLUSIONS: Prevertebral tendinitis should be considered when patients suffer from neck pain, neck stiffness, and globus sensations despite low signs of inflammation in the laboratory report. To confirm the diagnosis, the best imaging feature is magnetic resonance imaging with diffusion-weighted images and apparent diffusion coefficient map.

Congenital hearing loss explained in adulthood. Computed tomography of the temporal bone in hemifacial microsomia. A case report.

We present a case of complex hemifacial microsomia (HFM) which was diagnosed at the age of 46 years. Imaging findings of a complex deformity of the temporal bone are presented and connected to a broad range of clinical symptoms. Computed tomography (CT) imaging indications are discussed briefly.