A Molecular Strategy to Lock‐in the Conformation of a Perylene Bisimide‐Derived Supramolecular Polymer

Locking‐in the conformation of supramolecular assemblies provides a new avenue to regulate the (opto)electronic properties of robust nanoscale objects. In the present contribution, we show that the covalent tethering of a perylene bisimide (PBI)‐derived supramolecular polymer with a molecular locker enables the formation of a locked superstructure equipped with emergent structure–function relationships. Experiments that exploit variable‐temperature ground‐state electronic absorption spectroscopy unambiguously demonstrate that the excitonic coupling between nearest neighboring units in the tethered superstructure is preserved at a temperature (371 K) where the pristine, non‐covalent assembly exists exclusively in a molecularly dissolved state. A close examination of the solid‐state morphologies reveals that the locked superstructure engenders the formation of hierarchical 1D materials which are not achievable by unlocked assemblies. To complement these structural attributes, we further demonstrate that covalently tethering a supramolecular polymer built from PBI subunits enables the emergence of electronic properties not evidenced in non‐covalent assemblies. Using cyclic voltammetry experiments, the elucidation of the potentiometric properties of the locked superstructure reveals a 100‐mV stabilization of the conduction band energy when compared to that recorded for the non‐covalent assembly.     

Soil delta15N patterns in old-growth forests of southern Chile as integrator for N-cycling

Old-growth forests of southern Chile represent an important reserve of temperate (rain) forests in the world. Wetter and colder forest ecosystems appear to be more efficient in conserving and recycling N such that mostly non-plant available N species are lost, which could be indicated by more depleted delta15N values of the soil and plants. Hydrological N loss from the old-growth forests in southern Chile occurs mainly via dissolved organic nitrogen and not via dissolved inorganic N. Forest disturbances (e.g. fire, clear-cutting or enhanced N deposition) cause (abrupt) changes in ecosystem N-cycling processes. In this study, we hypothesized that delta15N signatures of soil profiles under old-growth forests could be used as an integrator for ecosystem N-cycling, and changes of these delta15N profiles could be valuable to assess ecosystem resilience towards disturbances. Six old-growth forests were selected in the phytogeographical region of the Valdivian rain forest in southern Chile. One of the sites has been partly burned in February 2002. First, we observed that ecosystems with higher mean annual precipitation and lower mean annual temperature were relatively more depleted in 15N. Secondly, we found that a forest fire caused a 100-fold increase of the nitrate export and induced an enrichment of the soil delta15N signal in the upper 20 cm.     

Numerical Analysis of the Behaviour of Tooth Intrarradial Posts by the Finite Element Method

The aim of this work is to study the behaviour of a carbon/epoxi post housed in a canine tooth after endodontic treatment in order to support the typical loads present during mastication. The three-D basic design of the dental piece consisting of tooth + post was carried out with a three-dimensional parametric design program. We study the stresses and displacements of the different elements of the dental piece under normal load conditions, and present the results and conclusions.     

Antiproliferative activity, antioxidant capacity and tannin content in plants of semi-arid northeastern Brazil

The objective of this study was to evaluate antiproliferative activity, antioxidant capacity and tannin content in plants from semi-arid northeastern Brazil (Caatinga). For this study, we selected 14 species and we assayed the methanol extracts for antiproliferative activity against the HEp-2 (laryngeal cancer) and NCI-H292 (lung cancer) cell lines using the (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazole) (MTT) method. In addition, the antioxidant activity was evaluated with the DPPH (2,2-diphenyl-2-picrylhydrazyl) assay, and the tannin content was determined by the radial diffusion method. Plants with better antioxidant activity (expressed in a dose able to decrease the initial DPPH concentration by 50%, or IC50) and with higher levels of tannins were: Poincianella pyramidalis (42.95±1.77 μg/mL IC50 and 8.17±0.64 tannin content), Jatropha mollissima (54.09±4.36μg/mL IC50 and 2.35±0.08 tannin content) and Anadenanthera colubrina (73.24±1.47 μg/mL IC50 and 4.41±0.47 tannin content). Plants with enhanced antiproliferative activity (% living cells) were Annona muricata (24.94±0.74 in NCI-H292), Lantana camara (25.8±0.19 in NCI-H292), Handroanthus impetiginosus (41.8±0.47 in NCI-H292) and Mentzelia aspera (45.61±1.94 in HEp-2). For species with better antioxidant and antiproliferative activities, we suggest future in vitro and in vivo comparative studies with other pharmacological models, and to start a process of purification and identification of the possible molecule(s) responsible for the observed pharmacological activity. We believe that the flora of Brazilian semi-arid areas can be a valuable source of plants rich in tannins, cytotoxic compounds and antioxidant agents.     

Pt-Cu / ZSM-5 for removal of nitrates from drinking water

Removal of nitrates from drinking water by catalytic hydrogenation over ZSM-5 supported Pt-Cu catalysts was studied. Bimetallics Pt-Cu were prepared by ion exchange of copper on a parent monometallic platinum catalyst. Monometallic platinum catalysts are inactive for nitrate reduction, while Pt-Cu bimetallic catalysts are active for nitrate removal. In the bimetallic catalyst, the role of copper is probably to reduce nitrate according to a redox reaction. The addition of copper to Pt catalysts decreases the production of ammonium ions     

Disk-shaped compact tension test for asphalt concrete fracture

A disk-shaped compact tension (DC(T)) test has been developed as a practical method for obtaining the fracture energy of asphalt concrete. The main purpose of the development of this specimen geometry is the ability to test cylindrical cores obtained from in-place asphalt concrete pavements or gyratory-compacted specimens fabricated during the mixture design process. A suitable specimen geometry was developed using the ASTM E399 standard for compact tension testing of metals as a starting point. After finalizing the specimen geometry, a typical asphalt concrete surface mixture was tested at various temperatures and loading rates to evaluate the proposed DC(T) configuration. The variability of the fracture energy obtained from the DC(T) geometry was found to be comparable with the variability associated with other fracture tests for asphalt concrete. The ability of the test to detect changes in the fracture energy with the various testing conditions (temperature and loading rate) was the benchmark for determining the potential of using the DC(T) geometry. The test has the capability to capture the transition of asphalt concrete from a brittle material at low temperatures to a more ductile material at higher temperatures. Because testing was conducted on ungrooved specimens, special care was taken to quantify deviations of the crack path from the pure mode I crack path. An analysis of variance of test data revealed that the prototype DC(T) can detect statistical differences in fracture energy resulting for tests conducted across a useful range of test temperatures and loading rates. This specific analysis also indicated that fracture energy is not correlated to crack deviation angle. This paper also provides an overview of ongoing work integrating experimental results and observations with numerical analysis by means of a cohesive zone model tailored for asphalt concrete fracture behavior.     

Geometric nonlinear analyses of functionally graded beams using a tailored Lagrangian formulation

This paper presents a geometric nonlinear analysis formulation for beams of functionally graded cross-sections by means of a Total Lagrangian formulation. The influence of material gradation on the numerical response is investigated in detail. Two examples are given that illustrate the main features of the formulation, in which the behavior of beams of graded cross-sections is compared with homogeneous material beams. A motivation for this work is the potential development of functionally graded risers for the offshore oil exploration industry.     

Microbial hydroxylation of sclareol by Rhizopus stolonifer

Incubation of sclareol with Rhizopus stolonifer affords in high yield a mixture of triols with 18-hydroxy-sclareol as the main component.     

Soil δ15N patterns in old-growth forests of southern Chile as integrator for N-cycling

Old-growth forests of southern Chile represent an important reserve of temperate (rain) forests in the world. Wetter and colder forest ecosystems appear to be more efficient in conserving and recycling N such that mostly non-plant available N species are lost, which could be indicated by more depleted δ¹⁵N values of the soil and plants. Hydrological N loss from the old-growth forests in southern Chile occurs mainly via dissolved organic nitrogen and not via dissolved inorganic N. Forest disturbances (e.g. fire, clear-cutting or enhanced N deposition) cause (abrupt) changes in ecosystem N-cycling processes. In this study, we hypothesized that δ¹⁵N signatures of soil profiles under old-growth forests could be used as an integrator for ecosystem N-cycling, and changes of these δ¹⁵N profiles could be valuable to assess ecosystem resilience towards disturbances. Six old-growth forests were selected in the phytogeographical region of the Valdivian rain forest in southern Chile. One of the sites has been partly burned in February 2002. First, we observed that ecosystems with higher mean annual precipitation and lower mean annual temperature were relatively more depleted in ¹⁵N. Secondly, we found that a forest fire caused a 100-fold increase of the nitrate export and induced an enrichment of the soil δ¹⁵N signal in the upper 20 cm.     

Inverse Estimation of Cohesive Fracture Properties of Asphalt Mixtures Using an Optimization Approach

Tensile cracking in asphalt pavements due to vehicular and thermal loads has become an experimental and numerical research focus in the asphalt materials community. Previous studies have used the discrete element method (DEM) to study asphalt concrete fracture. These studies used trial-and-error to obtain local fracture properties such that the DEM models approximate the experimental load-crack mouth opening displacement response. In the current study, we identify the cohesive fracture properties of asphalt mixtures via a nonlinear optimization method. The method encompasses a comparative investigation of displacement fields obtained using both digital image correlation (DIC) and heterogeneous DEM fracture simulations. The proposed method is applied to two standard fracture test geometries: the single-edge notched beam test, SE(B), under three-point bending, and the disk-shaped compact tension test, DC(T). For each test, the Subset Splitting DIC algorithm is used to determine the displacement field in a predefined region near the notch tip. Then, a given number of DEM simulations are performed on the same specimen. The DEM is used to simulate the fracture of asphalt concrete with a linear softening cohesive contact model, where fracture-related properties (e.g., maximum tensile force and maximum crack opening) are varied within a predefined range. The difference between DIC and DEM displacement fields for each set of fracture parameters is then computed and converted to a continuous function via multivariate Lagrange interpolation. Finally, we use a Newton-like optimization technique to minimize Lagrange multinomials, yielding a set of fracture parameters that minimizes the difference between the DEM and DIC displacement fields. The optimized set of fracture parameters from this nonlinear optimization procedure led to DEM results which are consistent with the experimental results for both SE(B) and DC(T) geometries.