Amide-Assisted Polymerization of 1,3-Butadiyne Containing Thiolate Ligands on Small Gold Nanoparticles.

Incorporation of directing amide groups has been shown to facilitate the topochemical polymerization of 1,3-butadiyne (diacetylene) groups in noncrystalline phases such as gels, amorphous solids, and liquid crystals. It remains challenging to polymerize 1,3-butadiyne-containing alkylthiolate ligands within their self-assembled monolayers on gold nanoparticles (AuNPs), which enhances their stability and adds new optical and electronic properties. Especially smaller AuNPs of sizes below 5 nm in diameter have been reported to display sluggish photopolymerization and are susceptible to photodegradation under UV irradiation. To probe the effectiveness of the amide-directed photopolymerization of 1,3-butadiyne ligands, small AuNPs in the 2-4 nm range were synthesized that contain alkylthiolate ligands with and without amide and 1,3-butadiyne groups. Their photopolymerization and photostability were studied by transmission electron microscopy (TEM), UV-vis spectroscopy, and Raman spectroscopy. AuNP with amide-free 1,3-butadiyne ligands templated the polymerization of the 1,3-butadiyne ligands but fused to large and insoluble particles during the polymerization process. AuNPs with ligands containing both 1,3-butadiyne and amide groups polymerized significantly faster, which slowed down photodegradation. A UV irradiation (254 nm and 176 W/m2) for 5-10 min was found to be optimal for the AuNPs with directing amide groups studied here, although their average core sizes grew from 3.8 to 4.0 nm in diameter and about 20% of the attached 1,3-butadiyne ligands remained unreacted after 10 minutes of irradiation. About 75% of the attached 1,3-butadiyne ligands were already polymerized during the first 5 min of UV irradiation. This decrease in reactivity is reasoned with a fast polymerization of ligands attached to facet sites and slower polymerization rates for ligands attached to edge and corner sites. Unexpectedly, photopolymerization occurred only in the presence of solvent, whereas no polydiacetylene was generated when dry powders of any of the diacetylene-containing gold nanoparticles were irradiated.

Synthesis and Characterization of Liquid-Crystalline Tetraoxapentacene Derivatives Exhibiting Aggregation-Induced Emission.

A series of new tetrakis(dialkoxyphenyl) dicyanotetraoxapentacene derivatives (1 a-c) were prepared by reaction of the appropriate terphenyl diols with tetrafluoroterephthalonitrile in good yields. Compounds 1 b and 1 c, which bear hexyloxy and decyloxy side chains, exhibited columnar hexagonal mesophases, as shown by polarized optical microscopy, variable-temperature powder X-ray diffraction, and differential scanning calorimetry. Single-crystal X-ray diffraction of methoxy-substituted 1 a revealed that the dicyanotetraoxapentacene core is highly planar, consistent with the notion that these molecules are able to stack in columnar mesophases. A detailed photophysical characterization showed that these compounds exhibit aggregation-induced emission in solution, emission in nonpolar solvents, weak emission in polar solvents, and strong emission in the solid state both as powder and in thin films. These observations are consistent with a weakly emissive charge-transfer state in polar solvents and a more highly emissive locally excited state in nonpolar solvents.

Topochemical Polymerization of a Nematic Tetraazaporphyrin Derivative To Generate Soluble Polydiacetylene Nanowires.

Polydiacetylenes are well-established one-dimensional organic semiconductors that have been generated by photochemical and thermal polymerizations of diacetylenes in single crystals, gel phases, thin films, and membranes. Their formation in mesophases, such as liquid crystals, has been surprisingly little studied although higher-ordered mesophases should support the topochemical polymerization of diacetylenes (1,3-butadiyne groups) and may give access to large domains of uniformly aligned materials. The polymerization of diacetylenes in a mesophase may also increase the stability of the self-assembled supramolecular structure. Here, the dye and discotic mesogen tetraazaporphyrin was decorated with eight diacetylene-containing alkyl chains to probe its mesomorphism and conversion into multifunctional polydiacetylene materials. While the incorporation of diacetylene groups supports columnar mesomorphism, successful photopolymerization required the presence of directing amide groups that suppressed columnar in favor of nematic mesomorphism. Still, the polymerization of the nematic mesophase generated a soluble nematic polydiacetylene of significantly higher molecular weight (Mn = 77 kDa or 25 monomer units by gel permeation chromatography) than what has been obtained in gel phases of related compounds. The formation of polydiacetylene was confirmed by Raman spectroscopy, and its nematic structure was verified by UV-vis spectroscopy, polarized optical microscopy, and X-ray diffraction. Both its nematic structure and the incorporation of eight side chains per discotic unit provide the polydiacetylene with sufficient solubility for casting thin films on substrates. Atomic force microscopy studies of films on silicon wafers revealed a grid-like structure of connected nanofibers. This study demonstrates the requirements for the formation of multifunctional mesomorphic polydiacetylene materials from mesomorphic precursors and their advantages. Optimization of the presented molecular design should give access to other mesophases and, consequently, functional polydiacetylene materials with tunable structures and optoelectronic properties.

Synthesis and Self-Assembly of Liquid Crystalline Triphenylenedicarboxythioimides.

We report the synthesis and properties of a series of novel triphenylenedicarboxyimides and thioimides (4-6) to probe the effect of thionation on the formation of columnar mesophases. These materials display broad columnar mesophases and high clearing points and self-associate in solution to form dimers. Overall, thionation improved the self-assembly in solution and led to a stabilization of the columnar mesophase. Furthermore, increasing the thionation of these materials led to a lowering of the lowest unoccupied molecular orbital (LUMO) energy level and a narrowing of the highest occupied molecular orbital-LUMO gap.

Distinct epitope structures of defensin-like proteins linked to proline-rich regions give rise to differences in their allergenic activity.

BACKGROUND: Art v 1, Amb a 4, and Par h 1 are allergenic defensin-polyproline-linked proteins present in mugwort, ragweed, and feverfew pollen, respectively. We aimed to investigate the physicochemical and immunological features underlying the different allergenic capacities of those allergens. METHODS: Recombinant defensin-polyproline-linked proteins were expressed in E. coli and physicochemically characterized in detail regarding identity, secondary structure, and aggregation status. Allergenic activity was assessed by mediator releases assay, serum IgE reactivity, and IgE inhibition ELISA using sera of patients from Austria, Canada, and Korea. Endolysosomal protein degradation and T-cell cross-reactivity were studied in vitro. RESULTS: Despite variations in the proline-rich region, similar secondary structure elements were observed in the defensin-like domains. Seventy-four percent and 52% of the Austrian and Canadian patients reacted to all three allergens, while Korean patients were almost exclusively sensitized to Art v 1. This was reflected by IgE inhibition assays demonstrating high cross-reactivity for Austrian, medium for Canadian, and low for Korean sera. In a subgroup of patients, IgE reactivity toward structurally altered Amb a 4 and Par h 1 was not changed suggesting involvement of linear epitopes. Immunologically relevant endolysosomal stability of the defensin-like domain was limited to Art v 1 and no T-cell cross-reactivity with Art v 125-36 was observed. CONCLUSIONS: Despite structural similarity, different IgE-binding profiles and proteolytic processing impacted the allergenic capacity of defensin-polyproline-linked molecules. Based on the fact that Amb a 4 demonstrated distinct IgE-binding epitopes, we suggest inclusion in molecule-based allergy diagnosis.

Readiness to reconcile and post-traumatic distress in German survivors of wartime rapes in 1945.

BACKGROUND: Sexual violence and wartime rapes are prevalent crimes in violent conflicts all over the world. Processes of reconciliation are growing challenges in post-conflict settings. Despite this, so far few studies have examined the psychological consequences and their mediating factors. Our study aimed at investigating the degree of longtime readiness to reconcile and its associations with post-traumatic distress within a sample of German women who experienced wartime rapes in 1945. METHODS: A total of 23 wartime rape survivors were compared to age- and gender-matched controls with WWII-related non-sexual traumatic experiences. Readiness to reconcile was assessed with the Readiness to Reconcile Inventory (RRI-13). The German version of the Post-traumatic Diagnostic Scale (PDS) was used to assess post-traumatic stress disorder (PTSD) symptomatology. RESULTS: Readiness to reconcile in wartime rape survivors was higher in those women who reported less post-traumatic distress, whereas the subscale "openness to interaction" showed the strongest association with post-traumatic symptomatology. Moreover, wartime rape survivors reported fewer feelings of revenge than women who experienced other traumatization in WWII. CONCLUSIONS: Our results are in line with previous research, indicating that readiness to reconcile impacts healing processes in the context of conflict-related traumatic experiences. Based on the long-lasting post-traumatic symptomatology we observed that our findings highlight the need for psychological treatment of wartime rape survivors worldwide, whereas future research should continue focusing on reconciliation within the therapeutic process.

[Structural and process quality in outpatient psychosocial cancer counselling centres. evaluating a major funding programme of the "Deutsche Krebshilfe e.V."]. / Struktur- und Prozessqualität in ambulanten psychosozialen Krebsberatungsstellen des Förderschwerpunktes "Psychosoziale Krebsberatung" der Deutschen Krebshilfe.

BACKGROUND: In 2007, the German Cancer Aid ("Deutsche Krebshilfe e.V.") initiated and funded a programme in 28 selected cancer counselling centres in Germany attempting to both promote and strengthen quality assured psychosocial cancer counselling as well as to ensure long-term financing. The accompanying evaluation programme aims to collect structural data of the institutions and to evaluate processes of quality assurance within the sample of cancer counselling centres. METHODS: On the basis of structured research within scientific databases and internet, as well as with the support of experts, characteristics of structural quality of cancer counselling centres were identified. Structural data were collected using a self-developed questionnaire and a semi-structured interview during the on-site visitations of the institutions. RESULTS: The results show homogeneity in some fields of structural quality such as individual psycho-oncological and social counselling, human resources, room facilities, quality assurance, diagnostics, documentation and public relations. Structural quality of the investigated centres appears more heterogeneous with regard to aspects such as availability and accessibility, barrier-free access, group support offers (counselling, sports, arts, etc.) as well as cooperation, financing and written mission statements. CONCLUSION: The investigated cancer counselling centres ensure mainly good minimum standards according to structural quality of cancer counselling. There is potential for further optimisation including cooperation, quality assurance, room facilities and being differentiated in terms of conceptual content and working concepts. Further achievements on quality assured cancer counselling can use the presented data as a basis for describing minimum standards and obligatory quality criteria.

[Detection of hearing loss in dementia patients : pilot study and literature survey]. / Detektion von Schwerhörigkeiten bei dementen Menschen : Pilotstudie und Literaturübersicht.

There is a higher incidence of dementia among people with hearing loss, although the complex interrelation is not yet understood. The potential influence of hearing rehabilitation is also unclear. A previously published retrospective study on this topic throws doubt on the ability of dementia patients to accomplish audiometric tests. Therefore, we conducted a pilot study to analyse the feasibility of applying conventional speech and pure tone audiometry in patients with dementia. In contrast to previously published data, we were able to achieve reproducible results in almost all patients. The difficulty associated with audiometric testing in dementia patients does thus not seem to lie in the application of pure tone and speech audiometry. On the basis of evidence indicating the importance of central hearing loss in the elderly, these tests alone do not appear sufficient. It is of greater interest to ascertain whether central hearing loss is relevant in patients suffering from dementia and whether corresponding audiometric tests are feasible.

[Dementia and otorhinolaryngologic practice]. / Der demente Patient in der HNO-Praxis.

The interaction between sensorial registration of peripheral stimuli and their central cognitive processing is not yet understood. The role of sensory deficits such as olfactory deterioration or hearing loss in the development of dementia is currently a focus of concern, with hopes of finding new diagnostic aspects and therapeutic options for multimodal treatment concepts in patients with dementia. The expertise of ENT specialists in the diagnostic and therapeutic fields of dysphagia, vestibular dysfunction and olfactory or hearing loss could make an important contribution to the development of future strategies for dealing with dementia. In this report we present up-to-date basic knowledge and ENT-specific aspects relating to the diagnostics and treatment of dementia.

[Hearing function and hearing loss in the elderly]. / Hörfähigkeit und Schwerhörigkeit alter Menschen.

Statistically, hearing function decreases with advancing age, but not all people are affected to the same extent. Environmental influences, such as noise exposure in particular, also play an important role in the development of hearing loss. Since the functional capacity of parts of the central auditory processing system can also diminish with age, these should also be evaluated in diagnostic procedures. Rehabilitative treatment of older people with hearing aids in particular, has to be improved. Audiotherapy can enhance the acceptance of hearing aids and optimize central auditory processing.

Mesomorphic [2]rotaxanes: sheltering ionic cores with interlocking components.

Two types of liquid crystalline [2]rotaxanes based on a conventional tetracatenar motif (a rod-shaped molecule with two side chains at each end) have been prepared. Dicationic compounds with ester stoppers and tetracationic materials with pyridinium stoppers are compared to each other and their dumbbell shaped analogs. Since the ionic core contributes about 70% to the overall length and molecular weight of the molecules, sheltering the ionic cores with an interlocked neutral macrocycle has considerable effect on the mesomorphism and thermal stability of the materials. The influence of the sheltering macrocycle, the numbers of charges on the core and the size and nature of the side chains (aliphatic vs siloxane) were probed. [2]Rotaxanes with linear side chains and minimum ratios of chain-to-core volumes of about 0.35 and 0.30 for tetra- and dicationic compounds, respectively, display smectic liquid crystal phases. Larger ratios increase the temperature range of the smectic A phases beyond the decomposition temperatures; a disadvantage for processing because no stable isotropic liquid phase is available. The change from tetra- to dicationic [2]rotaxanes increased not only the fluidity of their smectic A phases but also their thermal and chemical stability. Branched side chains (2-hexyldecyl) disfavor the formation of lamellar mesophases and, instead, induce higher ordered soft crystal phases. No liquid crystal phases but soft crystal phases are observed for the analogous di- and tetracationic compounds without an ion sheltering interlocked macrocycle (dumbbells).

New dihexadecyldithiophosphate SAMs on gold provide insight into the unusual dependence of adsorbate chelation on substrate morphology in SAMs of dialkyldithiophosphinic acids.

We report the formation and characterization of new self-assembled monolayers (SAMs) formed from dihexadecyldithiophosphate (C16)2DDP and compare their properties with those of SAMs formed from the structurally similar adsorbate dihexadecyldithiophosphinic acid (C16)2DTPA. The new (C16)2DDP SAMs were characterized using X-ray photoelectron spectroscopy, reflection-absorption infrared spectroscopy, contact angle measurements, and electrochemical impedance spectroscopy. The data indicate that (C16)2DDP forms SAMs on gold films formed by e-beam evaporation in which all adsorbates chelate to gold, in contrast to (C16)2DTPA SAMs, in which 40% of the adsorbates are monodentate. The alkyl chains of the (C16)2DDP SAM are also less densely packed and ordered than those of the (C16)2DTPA SAM. To understand these differences, we present density functional theory calculations that show that there are only minimal differences between the geometric and electronic structures of the two adsorbates and that the energetic difference between monodentate and bidentate binding of a gold(I) ion are surprisingly small for both adsorbates. This study leads to the conclusion that differences in intermolecular interactions within the SAM are the driving force for the difference in chelation between the two adsorbates.

Experimental and computational insights into the stabilization of low-valent main group elements using crown ethers and related ligands.

A series of tin(II) triflate and chloride salts in which the cations are complexed by either cyclic or acyclic polyether ligands and which have well-characterized single-crystal X-ray structures are investigated using a variety of experimental and computational techniques. Mössbauer spectroscopy illustrates that the triflate salts tend to have valence electrons with higher s-character, and solid-state NMR spectroscopy reveals marked differences between superficially similar triflate and chloride salts. Cyclic voltammetry investigations of the triflate salts corroborate the results of the Mössbauer and NMR spectroscopy and reveal substantial steric and electronic effects for the different polyether ligands. MP2 and DFT calculations provide insight into the effects of ligands and substituents on the stability and reactivity of the low-valent metal atom. Overall, the investigations reveal the existence of more substantial binding between tin and chlorine in comparison to the triflate substituent and provide a rationale for the considerably increased reactivity of the chloride salts.

Evaluation of a new optical measuring system for experiments on fractured human mandibles: a biomechanical feasibility study in maxillofacial surgery.

OBJECTIVES: Biomechanical loading on human mandibles was performed and a new optical measurement device was introduced for the quantification of interfragmentary movement in fractured mandibles stabilized with different osteosynthesis systems. MATERIALS AND METHODS: Comparison tests were performed with monocortical non-locking double plates and bicortical single locking plate. For the experiments on a specialized test bench, 18 ex vivo fractured human cadaveric mandibles were tested. Interfragmentary motion was detected in all three spatial dimensions using the optical measurement device PONTOS®. The movement was investigated over increasing incisal force and one summarized parameter was investigated. RESULTS: For the maximal tested load of 300 N m, the resultant interfragmentary movements in the two investigated groups were 2.96 ± 1.85° for the fixation with two conventional miniplates (six hole, profile 1.0 mm) and 4.53 ± 2.49° for single bicortically fixed locking plates (four hole, profile 1.5 mm). For both plate systems, we used the 2.0 mm screw system. CONCLUSIONS: The test bench in combination with the new optical device PONTOS(®) can test the primary stability of osteosynthesis. We offer a solution to the problem of rate of twist of the mandible as well as typical rotational problem in recent measurements. Further, the method can be used for development of new osteosynthesis products. CLINICAL RELEVANCE: Pseudoarthrosis formation is a common problem based on unsatisfying fixation of the fracture gap. The here presented combination of mechanical tests and numerical simulations can provide support for an improved treatment of fractured mandibles.

Perhydroazulene-based liquid-crystalline materials with smectic phases.

New liquid-crystalline materials with a perhydroazulene core were synthesized and the stereochemistry of these compounds was investigated. The mesomorphic properties of the new LC compounds were investigated by differential scanning colorimetry, polarizing optical microscopy and X-ray diffraction. We report here on the LC properties of nonchiral materials, which predominantly exhibit smectic phases and display nematic phases only within narrow temperature ranges. The dependence of the mesogenic behavior of the new materials on the stereochemistry of the core system was also investigated. All newly synthesized compounds were fully characterized by the usual spectroscopic and analytical methods.

Synthesis of 2,6-disubstituted tetrahydroazulene derivatives.

Synthesis of hydroazulene derivatives has been carried out through a ring-enlargement route by using carbene adduct intermediates. The protocol can be applied for the construction of functionalized hydroazulene skeletons as key components of many natural products as well as the core system of novel liquid-crystalline materials.

Columnar Mesomorphism of Board-Shaped Perylene, Diketopyrrolopyrrole, Isoindigo, Indigo, and Quinoxalino-Phenanthrophenazine Dyes.

The properties of organic dyes depend as much on their intermolecular interactions as on their molecular structure. While it is generally predictable what supramolecular structure would be ideal for a specific application, the generation of specific supramolecular structures by molecular design and suitable processing methods remains to be a challenge. A versatile approach to different supramolecular structures has been the application of mesomorphism in conjunction with alignment techniques and self-assembly at interfaces. Reviewed here is the columnar mesomorphism of board-shaped dyes perylene, indigo, isoindigo, diketopyrrolopyrrole, and quinoxalinophenanthrophenazine. They generate a larger number of different supramolecular structures than conventional disc-shaped (discotic) mesogens because of their non-circular shape and directional intermolecular interactions. The mesomorphism of all but the perylene derivatives is systematically and comprehensively covered for the first time.

The effect of incorporating Fréchet dendrons into rotaxanes and molecular shuttles containing the 1,2-bis(pyridinium)ethane⊂[24]crown-8 templating motif.

Fréchet-type dendrons (G0-G3) were added as both axle stoppering units and cyclic wheel appendages in a series of [2]rotaxanes, [3]rotaxanes, and molecular shuttles that employ 1,2-bis(pyridinium)ethane axles and 24-membered crown ethers wheels. The addition of dendrimer wedges as stoppering units dramatically increased the solubility of simple [2]rotaxanes in nonpolar solvents. The X-ray structure of a G1-stoppered [2]rotaxane shows how the dendritic units affect the structure of the interlocked components. Increased solubility allows observation of how the interaction of dendritic units on separate components in interlocked molecules influences switching properties and molecular size. In a series of [2]rotaxane molecular shuttles incorporating two recognition sites, it was demonstrated that an increase in generation on either the stoppering unit or cyclic wheel could influence both the rate of shuttling and the site preference of the wheel on the axle.

Quantitative ultrasound biomicroscopy for the analysis of healthy and repair cartilage tissue.

The increasing spectrum of different cartilage repair strategies requires the introduction of adequate non-destructive methods to analyse their outcome in-vivo, i.e. arthroscopically. The validity of non-destructive quantitative ultrasound biomicroscopy (UBM) was investigated in knee joints of five miniature pigs. After 12 weeks, six 5-mm defects, treated with different cartilage repair approaches, provided tissues with different structural qualities. Healthy articular cartilage from each contralateral unoperated knee joint served as a control. The reflected and backscattered ultrasound signals were processed to estimate the integrated reflection coefficient (IRC) and apparent integrated backscatter (AIB) parameters. The cartilage repair tissues were additionally assessed biomechanically by cyclic indentation, histomorphologically and immunohistochemically. UBM allowed high-resolution visualisation of the structure of the joint surface and subchondral bone plate, as well as determination of the cartilage thickness and demonstrated distinct differences between healthy cartilage and the different repair cartilage tissues with significant higher IRC values and a steeper negative slope of the depth-dependent backscatter amplitude AIBslope for healthy cartilage. Multimodal analyses revealed associations between IRC and the indentation stiffness. Furthermore, AIBslope and AIB at the cartilage-bone boundary (AIBdC) were associated with the quality of the repair matrices and the subchondral bone plate, respectively. This ex-vivo pilot study confirms that UBM can provide detailed imaging of articular cartilage and the subchondral bone interface also in repaired cartilage defects, and furthermore, contributes in certain aspects to a basal functional characterization of various forms of cartilage repair tissues. UBM could be further established to be applied arthroscopically in-vivo.