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.

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.

Simulation of SLA-based VM-scaling algorithms for cloud-distributed applications

Cloud Computing has evolved to become an enabler for delivering access to large scale distributed applications running on managed network-connected computing systems. This makes possible hosting Distributed Enterprise Information Systems (dEISs) in cloud environments, while enforcing strict performance and quality of service requirements, defined using Service Level Agreements (SLAs). {SLAs} define the performance boundaries of distributed applications, and are enforced by a cloud management system (CMS) dynamically allocating the available computing resources to the cloud services. We present two novel VM-scaling algorithms focused on dEIS systems, which optimally detect most appropriate scaling conditions using performance-models of distributed applications derived from constant-workload benchmarks, together with SLA-specified performance constraints. We simulate the VM-scaling algorithms in a cloud simulator and compare against trace-based performance models of dEISs. We compare a total of three SLA-based VM-scaling algorithms (one using prediction mechanisms) based on a real-world application scenario involving a large variable number of users. Our results show that it is beneficial to use autoregressive predictive SLA-driven scaling algorithms in cloud management systems for guaranteeing performance invariants of distributed cloud applications, as opposed to using only reactive SLA-based VM-scaling algorithms.

The Design and Synthesis of Versatile Molecular Building Blocks: Working Towards the Controlled Self-Assembly of Novel Functional Materials

Our research goals are focused on the preparation of novel molecule-based materials that possess specifically designed properties in solution or in the solid state e.g. self-assembly, magnetism, conductivity and spin crossover phenomena. Most of our systems incorporate paramagnetic transition metal ions and the search for new molecule-based magnetic materials is a prominent theme. Specific areas of research include the preparation and study of oxalate based 2D and 3D magnets, probing the versatility of octacyanometalate building blocks as precursors for new molecular magnets, and the preparation of new tetrathiafulvalene (TIF) derivatives for applications in molecular and supramolecular chemistry.

Cytotoxic effects of polycarbonate-based orthodontic brackets by activation of mitochondrial apoptotic mechanisms

OBJECTIVES: The aim of the study was to evaluate the biological effects of water eluents from polycarbonate based esthetic orthodontic brackets. METHODS: The composite polycarbonate brackets tested were Silkon Plus (SL, fiber-glass-reinforced), Elan ME (EL, ceramic particle-reinforced) and Elegance (EG, fiber-glass-reinforced). An unfilled polyoxymethylene bracket (Brilliant, BR) was used as control. The brackets' composition was analyzed by ATR-FTIR spectrometry. The cytotoxicity and estrogenicity of the eluents obtained after 3months storage of the brackets in water (37°C) were investigated in murine fibroblasts (NIH 3T3), breast (MCF-7) and cervical cancer (CCl-2/Hela) cell lines. RESULTS: SL and EG were based on aromatic-polycarbonate matrix, whereas EL consisted of an aromatic polycarbonate-polyethylene terepthalate copolymer. A significant induction of cell death and a concurrent decrease in cell proliferation was noted in the EG eluent-treated cells. Moreover, EG eluent significantly reduced the levels of the estrogen signaling associated gene pS2, specifically in MCF7 cells, suggesting that cell death induced by this material is associated with downregulation of estrogen signaling pathways. Even though oxidative stress mechanisms were equally activated by all eluents, the EG eluents induced expression of apoptosis inducing factor (AIF) and reduced Bcl-xL protein levels. SIGNIFICANCE: Some polycarbonate-based composite brackets when exposed to water release substances than activate mitochondrial apoptosis.

Genitourinary applications of diffusion-weighted MR imaging in the pelvis

Diffusion-weighted (DW) magnetic resonance (MR) imaging has a large number of potential clinical applications in the female and male pelvis and can easily be added to any routine MR protocol. In the female pelvis, DW imaging allows improvement of staging in endometrial and cervical cancer, especially in locally advanced disease and in patients in whom contrast medium administration should be avoided. It can also be helpful in characterizing complex adnexal masses and in depicting recurrent tumor after treatment of various gynecologic malignancies. DW imaging shows promising results in monitoring treatment response in patients undergoing radiation therapy of cervical cancer. An increase in apparent diffusion coefficient (ADC) values of responders precedes changes in size and may therefore allow early assessment of treatment success. In the male pelvis, the detection of prostate cancer in the peripheral zone is relatively easier than in the central gland based on the underlying ADC values, whereas overlapping values reported in the central gland still need further research. DW imaging might also be applied in the noninvasive evaluation of bladder cancer to differentiate between superficial and muscle-invasive tumors. Initial promising results have been reported in differentiating benign from malignant pelvic lymph nodes based on the ADC values; however, larger-scale studies will be needed to allow the detection of lymph node metastases in an individual patient. Prerequisites for successfully performing DW imaging of the female and male pelvis are standardization of the DW imaging technique, including the choice of b values, administration of an antiperistaltic drug, and comparison of DW findings with those of morphologic MR imaging.

Dynamic Optimization of SLA-Based Services Scaling Rules

Current advanced cloud infrastructure management solutions allow scheduling actions for dynamically changing the number of running virtual machines (VMs). This approach, however, does not guarantee that the scheduled number of VMs will properly handle the actual user generated workload, especially if the user utilization patterns will change. We propose using a dynamically generated scaling model for the VMs containing the services of the distributed applications, which is able to react to the variations in the number of application users. We answer the following question: How to dynamically decide how many services of each type are needed in order to handle a larger workload within the same time constraints? We describe a mechanism for dynamically composing the SLAs for controlling the scaling of distributed services by combining data analysis mechanisms with application benchmarking using multiple VM configurations. Based on processing of multiple application benchmarks generated data sets we discover a set of service monitoring metrics able to predict critical Service Level Agreement (SLA) parameters. By combining this set of predictor metrics with a heuristic for selecting the appropriate scaling-out paths for the services of distributed applications, we show how SLA scaling rules can be inferred and then used for controlling the runtime scale-in and scale-out of distributed services. We validate our architecture and models by performing scaling experiments with a distributed application representative for the enterprise class of information systems. We show how dynamically generated SLAs can be successfully used for controlling the management of distributed services scaling.

Comparison of globules prepared from high dilutions of various starting materials by ultraviolet light spectroscopy

Background: High and ultra-high dilutions of various starting materials, e.g. copper sulfate, Hypericum perforatum and sulfur, showed significant differences in ultraviolet light (UV) transmission from controls and amongst different dilution levels [1,2]. Verum and placebo globules of Aconitum napellus 30c or calcium carbonate/quercus e cortice 6x from the same packs as used in previous clinical trials and dissolved in water could be distinguished by UV spectroscopy [3]. However, it was unclear whether the differences in UV absorbance originated from specific characteristics of the starting materials, from differences in the production of verum and placebo globules, and/or other unknown interference factors. Aims: The aim of this study was to investigate whether globules produced with high and ultra-high dilutions (6x, 12x, 30c, 200c, 200CF (centesimal discontinuous fluxion), 10,000CF) of various starting materials (Aconitum napellus, Atropa belladonna, phosphorus, sulfur, Apis mellifica, quartz) could be distinguished by UV spectroscopy. Methodology: The globules were specially produced for this study by Spagyros AG (Gümligen, Switzerland) and differed only in the starting materials of the dilutions (but not in the batch of globules or ethanol used). Globules were dissolved in water at 10 mg/ml, in quadruplicates, approximately 22 h prior to the measurements. Absorbance of the samples in the UV range (from 190 to 340 nm) was measured in a randomized order with a Shimadzu double beam UV-1800 spectrophotometer equipped with an auto sampler. Samples of each starting material were prepared and measured on 5 independent days. The daily variations of the spectrophotometer as well as the drift during the measurements were corrected for. The average absorbance from 200 to 340 nm was compared among various starting materials within equal dilution levels using a Kruskal-Wallis test. Results: Statistically significant differences were found among 30c (Figure 1), 200c and 200CF dilutions of the various starting materials. No differences were found among 6x, 12x and 10,000CF dilutions. Conclusions: Globules prepared from high dilutions of various starting materials may show significantly different UV absorbance when dissolved in water. References [1] Wolf U, Wolf M, Heusser P, Thurneysen A, Baumgartner S. Homeopathic preparations of quartz, sulfur and copper sulfate assessed by UV-spectroscopy. Evid Based Complement Alternat Med. 2011;2011:692798. [2] Klein SD, Sandig A, Baumgartner S, Wolf U. Differences in median ultraviolet light transmissions of serial homeopathic dilutions of copper sulfate, Hypericum perforatum, and sulfur. Evid Based Complement Alternat Med. 2013;2013:370609. [3] Klein SD, Wolf U. Investigating homeopathic verum and placebo globules with ultraviolet spectroscopy. Forsch Komplementmed. 2013, accepted.

Influence of perylenediimide–pyrene supramolecular interactions on the stability of DNA-based hybrids: Importance of electrostatic complementarity

Aromatic pi–pi stacking interactions are ubiquitous in nature, medicinal chemistry and materials sciences. They play a crucial role in the stacking of nucleobases, thus stabilising the DNA double helix. The following paper describes a series of chimeric DNA–polycyclic aromatic hydrocarbon (PAH) hybrids. The PAH building blocks are electron-rich pyrene and electron-poor perylenediimide (PDI), and were incorporated into complementary DNA strands. The hybrids contain different numbers of pyrene–PDI interactions that were found to directly influence duplex stability. As the pyrene–PDI ratio approaches 1:1, the stability of the duplexes increases with an average value of 7.5 °C per pyrene–PDI supramolecular interaction indicating the importance of electrostatic complementarity for aromatic pi–pi stacking interactions.

Tracer applications of noble gas radionuclides in the geosciences

Noble gas radionuclides, including 81Kr (t1/2 = 229,000 years), 85Kr (t1/2 = 10.8 years), and 39Ar (t1/2 = 269 years), possess nearly ideal chemical and physical properties for studies of earth and environmental processes. Recent advances in Atom Trap Trace Analysis (ATTA), a laser-based atom counting method, have enabled routine measurements of the radiokrypton isotopes, as well as the demonstration of the ability to measure 39Ar in environmental samples. Here we provide an overview of the ATTA technique, and a survey of recent progress made in several laboratories worldwide.We review the application of noble gas radionuclides in the geosciences and discuss how ATTA can help advance these fields, specifically: determination of groundwater residence times using 81Kr, 85Kr, and 39Ar; dating old glacial ice using 81Kr; and an 39Ar survey of the main water masses of the oceans, to study circulation pathways and estimate mean residence times. Other scientific questions involving a deeper circulation of fluids in the Earth's crust and mantle are also within the scope of future applications. We conclude that the geoscience community would greatly benefit from an ATTA facility dedicated to this field, with instrumentation for routine measurements, as well as for research on further development of ATTA methods.

Technical complications and failures of zirconia-based prostheses supported by implants followed up to 7 years: a case series.

PURPOSE To evaluate technical complications and failures of zirconia-based fixed prostheses supported by implants. MATERIALS AND METHODS Consecutive patients received zirconia-based single crowns (SCs) and fixed dental prostheses (FDPs) on implants in a private clinical setting between 2005 and 2010. One dentist performed all surgical and prosthetic procedures, and one master technician performed and coordinated all laboratory procedures. One-piece computer-aided design/ computer-assisted manufacture technology was used to fabricate abutments and frameworks, which were directly connected at the implant level, where possible. All patients were involved in a recall maintenance program and were finally reviewed in 2012. Data on framework fractures, chipping of veneering ceramics, and other technical complications were recorded. The primary endpoint was failure of the prostheses, ie, the need for a complete remake. A life table analysis was calculated. RESULTS A total of 289 implants supported 193 zirconia-based prostheses (120 SCs and 73 FDPs) in 127 patients (51 men, 76 women; average age: 62.5 ± 13.4 years) who were reviewed in 2012. Twenty-five (13%) prostheses were cemented on 44 zirconia abutments and 168 (87%) prostheses were screw-retained directly at the implant level. Fracture of 3 frameworks (1 SC, 2 FDPs) was recorded, and significant chipping resulted in the remake of 3 prostheses (1 SC, 2 FDPs). The 7-year cumulative survival rate was 96.4% ± 1.99%. Minor complications comprised 5 loose screws (these were retightened), small chips associated with 3 prostheses (these were polished), and dislodgement of 3 prostheses (these were recemented). Overall, 176 prostheses remained free of technical problems. CONCLUSIONS Zirconia-based prostheses screwed directly to implants are clinically successful in the short and medium term.

A potential application of sludge-based catalysts for the anaerobic bio-decolorization of tartrazine dye.

Two highly efficient (K2CO3/sludge carbon and ZnCl2/sludge carbon) solids were prepared by chemical addition following carbonization at 800 °C and were tested for anaerobic reduction of tartrazine dye in a continuous upflow packed-bed biological reactor, and their performance was compared to that of commercial activated carbon (CAC). The chemical and structural information of the solids was subjected to various characterizations in order to understand the mechanism for anaerobic decolorization, and efficiency for SBCZN800 and SBCPC800 materials was 87% and 74%, respectively, at a short space time (τ) of 2.0 min. A first-order kinetic model fitted the experimental points and kinetic constants of 0.40, 0.92 and 1.46 min(-1) were obtained for SBCZN800, SBCPC800 and CAC, respectively. The experimental results revealed that performance of solids in the anaerobic reduction of tartrazine dye can depend on several factors including chemical agents, carbonization, microbial population, chemical groups and surface chemistry. The Langmuir and Freundlich models are successfully described in the batch adsorption data. Based on these observations, a cost-effective sludge-based catalyst can be produced from harmful sewage sludge for the treatment of industrial effluents.