From supramolecular sheets to fibers and back: establishing the critical parameters that govern the morphology of pyrene-based self-assembled materials

The precise arraying of functional entities in morphologically well-defined shapes remains one of the key challenges in the processing of organic molecules1. Among various π-conjugated species, pyrene exhibits a set of unique properties, which make it an attractive compound for the utilization in materials science2. In this contribution we report on properties of self-assembled structures prepared from amphiphilic pyrene trimers (Py3) consisting of phosphodiester-linked pyrenes. Depending on the geometry of a pyrene core substitution (1.6-, 1.8-, or 2.7- type, see Scheme), the thermally-controlled self-assembly allows the preparation of supramolecular architectures of different morphologies in a bottom-up approach: two-dimensional (2D) nanosheets3 are formed in case of 1.6- and 2.7-substitution4 whereas one-dimensional (1D) fibers are built from 1.8- substituted isomers. The morphologies of the assemblies are established by AFM and TEM, and the results are further correlated with spectroscopic and scattering data. Two-dimensional assemblies consist of an inner layer of hydrophobic pyrenes, sandwiched between a net of phosphates. Due to the repulsion of the negative charges, the 2D assemblies exist mostly as free-standing sheets. An internal alignment of pyrenes leads to strong exciton coupling with an unprecedented observation (simultaneous development of J- and H-bands from two different electronic transitions). Despite the similarity in spectroscopic properties, the structural parameters of the 2D aggregates drastically depend on the preparation procedure. Under certain conditions extra-large sheets (thickness of 2 nm, aspect ratio area/thickness ~107) in aqueous solution are formed4B. Finally, one-dimensional assemblies are formed as micrometer-long and nanometer-thick fibers. Both, planar and linear structures are intriguing objects for the creation of conductive nanowires that may find interest for applications in supramolecular electronics.

The benefits of one-dimensional detectors for high-pressure powder X-ray diffraction

High-pressure powder X-ray diffraction is a fundamental technique for investigating structural responses to externally applied force. Synchrotron sources and two-dimensional detectors are required. In contrast to this conventional setup, high-resolution beamlines equipped with one-dimensional detectors could offer much better resolved peaks but cannot deliver accurate structure factors because they only sample a small portion of the Debye rings, which are usually inhomogeneous and spotty because of the small amount of sample. In this study, a simple method to overcome this problem is presented and successfully applied to solving the structure of an L-serine polymorph from powder data. A comparison of the obtained high-resolution high-pressure data with conventional data shows that this technique, providing up to ten times better angular resolution, can be of advantage for indexing, for lattice parameter refinement, and even for structure refinement and solution in special cases.

Polaronic metal state at the LaAlO₃/SrTiO₃ interface

Interplay of spin, charge, orbital and lattice degrees of freedom in oxide heterostructures results in a plethora of fascinating properties, which can be exploited in new generations of electronic devices with enhanced functionalities. The paradigm example is the interface between the two band insulators LaAlO3 and SrTiO3 that hosts a two-dimensional electron system. Apart from the mobile charge carriers, this system exhibits a range of intriguing properties such as field effect, superconductivity and ferromagnetism, whose fundamental origins are still debated. Here we use soft-X-ray angle-resolved photoelectron spectroscopy to penetrate through the LaAlO3 overlayer and access charge carriers at the buried interface. The experimental spectral function directly identifies the interface charge carriers as large polarons, emerging from coupling of charge and lattice degrees of freedom, and involving two phonons of different energy and thermal activity. This phenomenon fundamentally limits the carrier mobility and explains its puzzling drop at high temperatures.

Evaluation of the maxillary sinus in panoramic radiography—a comparative study

Background: The aim of this study was to evaluate the validity and the inter- and intra-examiner reliability of panoramic-radiograph-driven findings of different maxillary sinus anatomic variations and pathologies, which had initially been prediagnosed by cone beam computed tomography (CBCT). Methods: After pairs of two-dimensional (2D) panoramic and three-dimensional (3D) CBCT images of patients having received treatment at the outpatient department had been screened, the predefinition of 54 selected maxillary sinus conditions was initially performed on CBCT images by two blinded consultants individually using a questionnaire that defined ten different clinically relevant findings. Using the identic questionnaire, these consultants performed the evaluation of the panoramic radiographs at a later time point. The results were analyzed for inter-imaging differences in the evaluation of the maxillary sinus between 2D and 3D imaging methods. Additionally, two resident groups (first year and last year of training) performed two diagnostic runs of the panoramic radiographs and results were analyzed for inter- and intra-observer reliability. Results: There is a moderate risk for false diagnosis of findings of the maxillary sinus if only panoramic radiography is used. Based on the ten predefined conditions, solely maxillary bone cysts penetrating into the sinus were frequently detected differently comparing 2D to 3D diagnostics. Additionally, on panoramic radiographs, the inter-observer comparison demonstrated that basal septa were significantly often rated differently and the intra-observer comparison showed a significant lack in reliability in detecting maxillary bone cysts penetrating into the sinus. Conclusions: Panoramic radiography provides the most information on the maxillary sinus, and it may be an adequate imaging method. However, particular findings of the maxillary sinus in panoramic imaging may be based on a rather examiner-dependent assessment. Therefore, a persistent and precise evaluation of specific conditions of the maxillary sinus may only be possible using CBCT because it provides additional information compared to panoramic radiography. This might be relevant for consecutive surgical procedures; consequently, we recommend CBCT if a precise preoperative evaluation is mandatory. However, higher radiation dose and costs of 3D imaging need to be considered. Keywords: Panoramic radiography; Cone beam computed tomography; Maxillary sinus; Inter-imaging method differences; Inter-examiner reliability; Intra-examiner reliability

Indications and Frequency for the Use of Cone Beam Computed Tomography for Implant Treatment Planning in a Specialty Clinic

PURPOSE To analyze the indications and frequency for three-dimensional (3D) imaging for implant treatment planning in a pool of patients referred to a specialty clinic over a 3-year period. MATERIALS AND METHODS All patients who received dental implants between 2008 and 2010 at the Department of Oral Surgery and Stomatology at the University of Bern were included in the study. The influence of age, gender, and time of treatment (2008 to 2010) on the frequency of use of two-dimensional (2D) radiographic imaging modalities alone or in combination with 3D cone beam computed tomography (CBCT) scans was analyzed. Furthermore, the influence of the indication, location, and need for bone augmentation on the frequency of use of 2D imaging modalities alone or in combination with CBCT was evaluated. RESULTS In all, 1,568 patients (792 women and 776 men) received 2,279 implants. Overall, 633 patients (40.4%) were analyzed with 2D imaging procedures alone. CBCT was performed in 935 patients (59.6%). There was a statistically significant increase in CBCT between 2008 and 2010. Patients older than 55 years received a CBCT scan in addition to 2D radiographic imaging statistically significantly more often. Additional 3D imaging was most frequently performed in the posterior maxilla, whereas 2D radiographs alone exhibited the highest frequency in the anterior mandible. The combination of 2D with CBCT was used predominantly for implant placement with simultaneous or staged guided bone regeneration or sinus elevation. CONCLUSION Based on these findings from a specialty clinic, the use of additional CBCT imaging for implant treatment planning is influenced by the indication, location, local anatomy (including the need for bone augmentation), and the age of the patient.