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.

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.

Stabilization of Columnar Liquid Crystal Phases via Arene-Perfluoroarene Interactions.

We report the synthesis of novel polycatenar dibenzopentacenequinones 1 and 2 that are designed to form columnar liquid crystalline phases. The mesomorphic properties of these compounds were investigated by polarized optical microscopy, differential scanning calorimetry, and powder X-ray diffraction. While compound 1 exhibits two distinct columnar mesophases between 148 and 177 °C, fluorinated 2 exhibits a columnar mesophase from 121 to 336 °C. This dramatic stabilization of the columnar mesophase of 2 can be attributed to improved π-stacking as a result of arene-perfluoroarene interactions.

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.

Development and validation of a measurement system for continuously monitoring postoperative reservoir levels.

Following cardiac surgical procedures, multiple drainage systems remain in place inside the patient's chest to prevent the development of pericardial effusion or pneumothorax. Therefore, postoperative bleeding must be diligently observed. Currently, observation of the exudate rate is performed through periodical visual inspection of the reservoir. To improve postoperative monitoring, a measurement system based on load cells was developed to automatically detect bleeding rates. A reservoir retaining bracket was instrumented with a load cell. The signal was digitized by a microcontroller and then processed and displayed on customized software written in LabView. In cases where bleeding rates reach critical levels, the device will automatically sound an alarm. Additionally, the bleeding rate is displayed on the screen with the status of the alarm, as well as the fluid level of the reservoir. These data are all logged to a file. The measurement system has been validated for gain stability and drift, as well as for sensor accuracy, with different in vitro examinations. Additionally, performance of the measurement device was tested in a clinical pilot study on patients recovering from cardiac surgical procedures. The in vitro investigation showed that the monitoring device had excellent gain and drift stability, as well as sensor accuracy, with a resolution of 2.6 mL/h for the bleeding rate. During the clinical examination, bleeding rates of all patients were correctly measured. Continuously recording drainage volume using the developed system was comparable to manual measurements performed every 30 min by a nurse. Implementation of continuous digital measurements could improve patient safety and reduce the workload of medical professionals working in intensive care units.

Self-Assembly of Board-Shaped Diketopyrrolopyrrole and Isoindigo Mesogens into Columnar π-π Stacks.

Diketopyrrolopyrrole and isoindigo are commercially important dyes that have recently found broad application as electron acceptor and light-absorbing groups in organic semiconductors. Their self-assembly into specific supramolecular structures to control optoelectronic properties has been hampered by limited options for substitution and their high propensity for crystallization. Reported here is a molecular design that directs self-assembly into previously elusive columnar mesophases of π-π stacking cores. Although attachment of bis(trisoctyloxyphenyl)-1,3,5-triazine groups to both ends of diketopyrrolopyrrole-thiophene and isoindigo cores generated mesomorphic dyes of similar overall shapes and dimensions, distinct differences in their mesomorphism and optoelectronic properties were observed.

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.

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.

Corpuls cpr resuscitation device generates superior emulated flows and pressures than LUCAS II in a mechanical thorax model.

The provision of sufficient chest compression is among the most important factors influencing patient survival during cardiopulmonary resuscitation (CPR). One approach to optimize the quality of chest compressions is to use mechanical-resuscitation devices. The aim of this study was to compare a new device for chest compression (corpuls cpr) with an established device (LUCAS II). We used a mechanical thorax model consisting of a chest with variable stiffness and an integrated heart chamber which generated blood flow dependent on the compression depth and waveform. The method of blood-flow generation could be changed between direct cardiac-compression mode and thoracic-pump mode. Different chest-stiffness settings and compression modes were tested to generate various blood-flow profiles. Additionally, an endurance test at high stiffness was performed to measure overall performance and compression consistency. Both resuscitation machines were able to compress the model thorax with a frequency of 100/min and a depth of 5 cm, independent of the chosen chest stiffness. Both devices passed the endurance test without difficulty. The corpuls cpr device was able to generate about 10-40% more blood flow than the LUCAS II device, depending on the model settings. In most scenarios, the corpuls cpr device also generated a higher blood pressure than the LUCAS II. The peak compression forces during CPR were about 30% higher using the corpuls cpr device than with the LUCAS II. In this study, the corpuls cpr device had improved blood flow and pressure outcomes than the LUCAS II device. Further examination in an animal model is required to prove the findings of this preliminary study.

Corpuls CPR Generates Higher Mean Arterial Pressure Than LUCAS II in a Pig Model of Cardiac Arrest.

According to the European Resuscitation Council guidelines, the use of mechanical chest compression devices is a reasonable alternative in situations where manual chest compression is impractical or compromises provider safety. The aim of this study is to compare the performance of a recently developed chest compression device (Corpuls CPR) with an established system (LUCAS II) in a pig model. Methods. Pigs (n = 5/group) in provoked ventricular fibrillation were left untreated for 5 minutes, after which 15 min of cardiopulmonary resuscitation was performed with chest compressions. After 15 min, defibrillation was performed every 2 min if necessary, and up to 3 doses of adrenaline were given. If there was no return of spontaneous circulation after 25 min, the experiment was terminated. Coronary perfusion pressure, carotid blood flow, end-expiratory CO2, regional oxygen saturation by near infrared spectroscopy, blood gas, and local organ perfusion with fluorescent labelled microspheres were measured at baseline and during resuscitation. Results. Animals treated with Corpuls CPR had significantly higher mean arterial pressures during resuscitation, along with a detectable trend of greater carotid blood flow and organ perfusion. Conclusion. Chest compressions with the Corpuls CPR device generated significantly higher mean arterial pressures than compressions performed with the LUCAS II device.

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.

Automation of a portable extracorporeal circulatory support system with adaptive fuzzy controllers.

The presented work relates to the procedure followed for the automation of a portable extracorporeal circulatory support system. Such a device may help increase the chances of survival after suffering from cardiogenic shock outside the hospital, additionally a controller can provide of optimal organ perfusion, while reducing the workload of the operator. Animal experiments were carried out for the acquisition of haemodynamic behaviour of the body under extracorporeal circulation. A mathematical model was constructed based on the experimental data, including a cardiovascular model, gas exchange and the administration of medication. As the base of the controller fuzzy logic was used allowing the easy integration of knowledge from trained perfusionists, an adaptive mechanism was included to adapt to the patient's individual response. Initial simulations show the effectiveness of the controller and the improvements of perfusion after adaptation.

Influence of Chromophore Length and Acceptor Groups on the Optical Properties of Rigidified Merocyanine Dyes.

Invited for this month's cover are the three collaborating groups from the University of Stuttgart and the Fraunhofer Institute for Applied Polymer Research in Potsdam, both from Germany as well as the University of Windsor, Canada. The cover picture shows the shift of frontier orbital energies and symmetries upon excitation with light for three different chromophore lengths. Read the full text of the article at 10.1002/cplu.201300308.

Influence of Chromophore Length and Acceptor Groups on the Optical Properties of Rigidified Merocyanine Dyes.

Three series of rigidified tri-, penta- and heptamethine merocyanine dyes were synthesised. A piperidyl moiety was chosen as the electron-donating substituent while the electron-accepting group was varied from ketones to malononitriles and cyanoacetates. The structures of the compounds in the solid state and in solution were elucidated by X-ray diffraction and NMR spectroscopy, respectively, while optical properties were investigated by absorption and emission spectroscopy. As a general trend, the acceptor properties decrease in the series malononitrile>cyanoacetate>ketone based on the analysis of their solvatochromic behaviour. The experimental results were further supported by calculations at the B3LYP 6-311+G(d) level of theory.