Tubes or sheets: divergent aggregation pathways of an amphiphilic 2,7-substituted pyrene trimer

The self-assembly of an amphiphilic 2,7-linked pyrene trimer in an aqueous environment into two morphologically related forms is described. Supramolecular polymerization leads to the simultaneous formation of nanosheets and nanotubes.

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.

Bone-added periodontal plastic surgery: a new approach in esthetic dentistry

This article proposes a combined technique including bone grafting, connective tissue graft, and coronally advanced flap to create some space for simultaneous bone regrowth and root coverage. A 23 year-old female was referred to our private clinic with a severe class II Miller recession and lack of attached gingiva. The suggested treatment plan comprised of root coverage combined with xenograft bone particles. The grafted area healed well and full coverage was achieved at 12-month follow-up visit. Bone-added periodontal plastic surgery can be considered as a practical procedure for management of deep gingival recession without buccal bone plate.

An international assessment of the comprehensibility of material safety data sheets (MSDSs)

Material Safety Data Sheets (MSDSs) are an integral component of occupational hazard communication systems. These documents are used to disseminate hazard information to workers on chemical substances. The primary purpose of this study was to investigate the comprehensibility of MSDSs by workers at an international level. ^ A total of 117 employees of a multi-national petrochemical company participated; thirty-nine (39) each in the United States, Canada and the United Kingdom. Overall participation rate of those approached to participate was 82%. These countries were selected as they each utilize one of the three major existing hazard communication systems for fixed workplaces. The systems are comprised of the Occupational Safety and Health Administration's Hazard Communication Standard in the United States, the Workplace Hazardous Materials Information System (WHMIS) in Canada, and the compilation of several European Union directives addressing classification, labeling of substances and preparations, and MSDSs in Europe. ^ A pretest posttest randomized study design was used, with the posttest being comparable to an open book test. The results of this research indicated that only about two-thirds of the information on the MSDSs was comprehended by the workers with a significant difference identified among study participants based on country comparisons. This data was fairly consistent with the results of previous MSDS comprehensibility studies conducted in the United States. There was no significant difference in the comprehension level among study participants when taking into account the international hazard communication standard that the MSDS complied with. Marginally, age, education level and experience level did not have a significant impact on the comprehension level. ^ Participants did find MSDSs to be satisfactory in providing the information needed to protect them regardless of their views on the readability and formatting of MSDSs. The health-related information was the least comprehended as less than half of it was comprehended on the basis of the responses. The findings from this research suggest that there is much work needed yet to make MSDSs more comprehensible on a global basis, particularly regarding health-related information. ^

Black Degradable Plastic Mulch Evaluation

Black polyethylene plastic mulch provides many benefits to fruit and vegetable producers. It increases earliness by increasing spring soil temperatures, conserves soil moisture, and reduces pesticide usage by decreasing weed and disease pressure. Furthermore, during seasons of high precipitation, it protects fertilizer from leaching below the root zone. Unfortunately, polyethylene mulches do not degrade and must be removed from the field and discarded each season. This is a labor-intensive process whether it is done mechanically or by hand. Several degradable plastic mulches have been developed that are designed to be incorporated into the soil profile, eliminating the need for removal, with no negative impact on soil quality or health. However, these degradable plastics often do not meet degradation expectations (either degrade too quickly or degrade incompletely and require manual removal). The objective of this project was to evaluate several degradable mulches for storage life, ease of use, and influence on tomato production.

A numerical discrete element study on the influence of an embedded viscoelastic-plastic layer at different viscosity values

The major aim of this study was to examine the influence of an embedded viscoelastic-plastic layer at different viscosity values on accretionary wedges at subduction zones. To quantify the effects of the layer viscosity, we analysed the wedge geometry, accretion mode, thrust systems and mass transport pattern. Therefore, we developed a numerical 2D 'sandbox' model utilising the Discrete Element Method. Starting with a simple pure Mohr Coulomb sequence, we added an embedded viscoelastic-plastic layer within the brittle, undeformed 'sediment' package. This layer followed Burger's rheology, which simulates the creep behaviour of natural rocks, such as evaporites. This layer got thrusted and folded during the subduction process. The testing of different bulk viscosity values, from 1 × 10**13 to 1 × 10**14 (Pa s), revealed a certain range where an active detachment evolved within the viscoelastic-plastic layer that decoupled the over- and the underlying brittle strata. This mid-level detachment caused the evolution of a frontally accreted wedge above it and a long underthrusted and subsequently basally accreted sequence beneath it. Both sequences were characterised by specific mass transport patterns depending on the used viscosity value. With decreasing bulk viscosities, thrust systems above this weak mid-level detachment became increasingly symmetrical and the particle uplift was reduced, as would be expected for a salt controlled forearc in nature. Simultaneously, antiformal stacking was favoured over hinterland dipping in the lower brittle layer and overturning of the uplifted material increased. Hence, we validated that the viscosity of an embedded detachment strongly influences the whole wedge mechanics, both the respective lower slope and the upper slope duplex, shown by e.g. the mass transport pattern.

Concentrations of floating plastic debris in the Mediterranean Sea measured during MedSeA-2013 cruise

Floating plastic debris sampled in surface waters of the Mediterranean Sea in May 2013 on board the Spanish R/V Angeles Alvariño. Geographical coordinates and dates of sampling are available in the dataset. Surface plastic concentrations derived from net tows were adjusted in relation to wind speed following the vertical-distribution model proposed by Kukulta et al. (2012, doi:10.1029/2012GL051116).

DATED-1: compilation of dates and time-slice reconstruction of the build-up and retreat of the last Eurasian (British-Irish, Scandinavian, Svalbard-Barents-Kara Seas) Ice Sheets 40-10 ka

DATED-1 comprises a compilation of dates related to the build-up and retreat of the Eurasian (British-Irish, Scandinavian, Svalbard-Barents-Kara Seas) Ice Sheets, and time-slice maps of the Eurasian Ice sheet margins. Dates are sourced from the published literature. Ice margins are based on published geological and chronological data and include uncertainty bounds (maximum, minimum) as well as what we consider to be the most-credible (mc) based on the available evidence. DATED-1 has a census date of 1 January 2013. Full description and caveats for use are given in: Hughes, A.L.C., Gyllencreutz, R., Lohne, Ø.S., Mangerud, J., Svendsen, J.I. (2015) The last Eurasian Ice Sheets - a chronological database and time-slice reconstruction, DATED-1.

The number of plastic particles found in estuarine sediment and water samples of five estuaries, Durban, KwaZulu-Natal, South Africa

Widespread disposal of plastics negatively affects biotic and abiotic components of marine systems. Monitoring plastics transitioning through estuaries is vital in assessing terrestrial inputs to oceanic environments. Data on microplastics (particles <= 5mm) in estuaries are scant. This study determined microplastic levels within five estuaries along the Durban coastline and on intervening beaches. Plastics were isolated from estuarine sediment, beach sediment and the surface water of each estuary and characterised. Sediment at the Bayhead area of Durban Harbour was found to contain the highest average plastic concentrations (745.40 ± 129.72 particles per 500ml). Overall an attenuating concentration trend away from the city center was found. Fragments composed the largest percent of plastics (59 %) found in Bayhead, whereas fibers dominated other estuaries (Mdloti - 66 %, uMgeni - 38 %, Isipingo - 45 % and iLovu - 53 %). Plastic particle concentration in estuarine sediment generally increased from larger to smaller size classes. If high input and high retention in the harbour is coupled with high organic and metal pollutant loads, this area can become (if not already) a major environmental hazard.

Wave-induced changes in seaweed toughness entail plastic modifications in snail traits maintaining consumption efficacy, link to supplementary material

1. Environmental stress can influence species traits and performance considerably. Using a seaweed-snail system from NW (Nova Scotia) and NE (Helgoland) Atlantic rocky shores, we examined how physical stress (wave exposure) modulates traits in the seaweed Fucus vesiculosus and indirectly in its main consumer, the periwinkle Littorina obtusata. 2. In both regions, algal tissue toughness increased with wave exposure. Reciprocal-transplant experiments showed that tissue toughness adjusts plastically to the prevailing level of wave exposure. 3. Choice experiments tested the feeding preference of snails from sheltered, exposed, and very exposed habitats for algae from such wave exposures. Snails from exposed and very exposed habitats consumed algal tissues at similar rates irrespective of the exposure of origin of the algae. However, snails from sheltered habitats consumed less algal tissues from very exposed habitats than tissues from sheltered and exposed habitats. Choice assays using reconstituted algal food (triturated during preparation) identified high thallus toughness as the explanation for the low preference of snails from sheltered habitats for algae from very exposed habitats. 4. Ultrastructural analyses of radulae indicated that rachidian teeth were longest and the number of cusps in lateral teeth (grazing-relevant traits) was highest in snails from very exposed habitats, suggesting that radulae are best suited to rupture tough algal tissues in such snails. 5. No-choice feeding experiments revealed that these radular traits are also phenotypically plastic, as they adjust to the toughness of the algal food. 6. Synthesis. This study indicates that the observed plasticity in the feeding ability of snails is mediated by wave exposure through phenotypic plasticity in the tissue toughness of algae. Thus, plasticity in consumers and their resource species may reduce the potential effects of physical stress on their interaction.

Laser Shock Microformingof Thin Metal Sheets with ns Lasers

Continuous and long-pulse lasers have been used for the forming of metal sheets in macroscopic mechanical applications. However, for the manufacturing of micro-electromechanical systems (MEMS), the use of ns laser pulses provides a suitable parameter matching over an important range of sheet components that, preserving the short interaction time scale required for the predominantly mechanical (shock) induction of deformation residual stresses, allows for the successful processing of components in a medium range of miniaturization without appreciable thermal deformation.. In the present paper, the physics of laser shock microforming and the influence of the different experimental parameters on the net bending angle are presented.

Development of Robotized Laser Welding Applications for Joining Thin Sheets

Laser Welding (LW) is more often used in manufacturing due to its advantages, such as accurate control, good repeatability, less heat input, opportunities for joining of special materials, high speed, capability to join small dimension parts etc. LW is dedicated to robotized manufacturing, and the fabrication cells are using various level of flexibility, from specialized robots to very flexible setups. This paper features several LW applications using two industrially-scaled manufacturing cells at UPM Laser Centre (CLUPM) of Polytechnical University of Madrid (Universidad Politécnica de Madrid). The one dedicated to Remote Laser Welding (RLW) of thin sheets for automotive and other sectors uses a CO2 laser of 3500 W. The second has a high flexibility, is based on a 6-axis ABB robot and a Nd:YAG laser of 3300 W, and is meant for various laser processing methods, including welding. After a short description of each cell, several LW applications experimented at CLUPM and recently implemented in industry are briefly presented: RLW of automotive coated sheets, LW of high strength automotive sheets, LW vs. laser hybrid welding (LHW) of Double Phase steel thin sheets, and LHW of thin sheets of stainless steel and carbon steel (dissimilar joints). The main technological issues overcame and the critical process parameters are pointed out. Conclusions about achievements and trends are provided.