Pollution control quasi-equilibrium problems with joint implementation of environmental projects

In this paper, we show how one of the Kyoto Protocol mechanisms, the so-called joint implementation in environmental projects, can be transformed into and studied as an infinite-dimensional quasi-variational inequality. Specifically, we examine the situation in which different countries attempt to fulfill Kyoto commitments by investing in emission reduction or emission removal projects in countries where the abatement costs are lower. We derive the equilibrium conditions and prove their characterization in terms of an infinite-dimensional quasi-variational inequality problem. Finally, we discuss the existence of solutions.     

Antioxidant potential and authenticity of some commercial fruit juices studied by EPR and IRMS

Antioxidant status of foods, plant, or fruit products is generally characterized by means of spectroscopic methods. Methods like HPLC, UV-VIS, or MS spectroscopy are used to understand the chemical and physical properties of different samples, and also EPR spectroscopy seems to be a valuable tool to characterize antioxidant activity of juice beverages. In this technique, certain antioxidants present in fruit juices interact with free radicals interrupting the chain reaction that can possibly damage essential molecules. Recording the EPR signal decay caused by the reaction with a natural or artificial reducing agent, it is possible to draw conclusions about the antioxidant capability of materials. IRMS is a powerful tool to distinguish between an authentic fruit juice and a juice obtained by concentrate dilution. This technique allows also the detection of commercial C₄ cane or corn derived sugar syrups in C₃ fruit juices. In the present study, four commercial fruit juices were investigated using stable isotope measurements (oxygen, hydrogen, and carbon) and EPR measurements in order to check the correct labeling in the Romanian markets and to compare antioxidant activity of the studied juices and the reference. It was proven that the number of paramagnetic species decreases in time with different reaction rates and this was correlated with the antioxidant activity of the studied juices. Stable isotope ratio measurements have demonstrated that the fruit juices studied were reconstructed from concentrates with tap water, according to their label.     

Does shape matter? Bioeffects of gold nanomaterials in a human skin cell model

Gold nanomaterials (AuNMs) have distinctive electronic and optical properties, making them ideal candidates for biological, medical, and defense applications. Therefore, it is imperative to evaluate the potential biological impact of AuNMs before employing them in any application. This study investigates two AuNMs with different aspect ratios (AR) on mediation of biological responses in the human keratinocyte cell line (HaCaT) to model potential skin exposure to these AuNMs. The cellular responses were evaluated by cell viability, reactive oxygen species (ROS) generation, alteration in gene and protein expression, and inflammatory response. Gold nanospheres, nominally 20 nm in diameter and coated with mercaptopropane sulfonate (AuNS-MPS), formed agglomerates when dispersed in cell culture media, had a large fractal dimension (D(f) = 2.57 ± 0.4) (i.e., tightly bound and densely packed) and were found to be nontoxic even at the highest dose of 100 μg/mL. Highly uniform, 16.7 nm diameter, and 43.8 nm long polyethylene glycol-capped gold nanorods (AuNR-PEG) also formed agglomerates when dispersed into the cell culture media. However, the agglomerates had a smaller fractal dimension (D(f) = 1.28 ± 0.08) (i.e., loosely bound) and were found to be cytotoxic to the HaCaT cells, with a significant decrease in cell viability occurring at 25 μg/mL and higher. Moreover, AuNR-PEG caused significant ROS production and up-regulated several genes involved in cellular stress and toxicity. These results, combined with increased levels of inflammatory and apoptotic proteins, demonstrated that the AuNR-PEG induced apoptosis. Exposure to AuNS-MPS, however, did not show any of the detrimental effects observed from the AuNR-PEG. Therefore, we conclude that shape appears to play a key role in mediating the cellular response to AuNMs.     

Self-assembly of doublets from flattened polymer colloids

Bottom-up fabrication methods are used to assemble strong yet flexible colloidal doublets. Part of a spherical particle is flattened, increasing the effective interaction area with another particle having a flat region. In the presence of a moderate ionic strength, the flat region on one particle will preferentially "bond" to a flat region on another particle in a deep (≥10 kT) secondary energy minimum. No external field is applied during the assembly process. Under the right conditions, the flat-flat bonding strength is ≥10× that of a sphere-sphere interaction. Not only can flat-flat bonds be quite strong, but they are expected to remain freely rotatable and flexible, with negligible energy barriers for rotation because particles reside in a deep secondary energy minimum with a ~20-30 nm layer of fluid between the ~1 μm radius particles. We present a controlled technique to flatten the particles at room temperature, the modeling of the interparticle forces for flattened spheres, and the experimental data for the self-assembly of flat-flat doublets.     

Hierarchised luminescent organic architectures: design, synthesis, self-assembly, self-organisation and functions

This critical review aims at highlighting the prevailing supramolecular approaches employed nowadays in the preparation of luminescent hierarchised materials. Specifically, it has the ambition to illustrate how progresses in the control of the supramolecular interaction toolbox ultimately led to the development of spectacular luminescent nano- and micro-architectures, through a combination of molecular self-assembly and self-organisation processes involving organic π-conjugated molecules. The reader will be guided through a systematic exploration of the most common avenues to prepare and characterise luminescent self-assembled/self-organised materials embedded into one-, two- or three-dimensional networks, accompanied by a critical discussion of their main advantages and limitations. Key representative examples of this research field will be thoroughly described, with a particular focus on those systems displaying potential on the device application scene. Particular attention will be devoted to the design and synthetic approaches aimed at the preparation of the primary π-conjugated molecular modules, the chemical, structural and electronic properties of which dramatically influence the fate and the features of the self-assembled/self-organised material (215 references).     

ESI-MS and MALLS analysis of quaternary structure of molluscan hemocyanins

The understanding of the function of macromolecular complexes is mainly related to a precise knowledge of their structure. Recently, the development of suitable mass spectrometric techniques (electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI)) and multi-angle laser light scattering has enabled mass determination of native complexes and of their subunits. By these techniques, the structure and association/dissociation behavior of huge molecules of molluscan Octopus vulgaris, Sepia officinalis and Rapana venosa have been characterized. Molecular masses of the native and dissociated molecule of cephalopodan Hcs O. vulgaris (3545 and 359.3?kDa, respectively) and S. officinalis (4134 and 443.8?kDa, respectively) revealed that only one type subunit organizes their molecules, while the presence of two isoforms with different masses (422.8 and 400.0?kDa) has been determined for gastropodan R. venosa Hc, aggregated into didecamers. The difference of their structural subunits was also established after limited proteolysis with TPCK-trypsin. Eight functional units (FUs) with masses of?~?50?kDa were isolated from both subunits of RvH and isoform of Sepia officinalis, while seven FUs were purified from OvH. Further characterization of proteins by ESI-mass spectrometry (MS) and MALDI-MS, methods gave insights into post-translational modifications such as glycosylation. Glycosylation of O. vulgaris and S. officinalis Hcs was suggested based on the differences (11.6 and 40.0?kDa, respectively) between the masses measured by ESI-MS and those calculated by their gene sequences.     

Gender effect on neurodegeneration and myelin markers in an animal model for multiple sclerosis

Background  

Multiple sclerosis (MS) varies considerably in its incidence and progression in females and males. In spite of clinical evidence, relatively few studies have explored molecular mechanisms possibly involved in gender-related differences. The present study describes possible cellular- and molecular-involved markers which are differentially regulated in male and female rats and result in gender-dependent EAE evolution and progression. Attention was focused on markers of myelination (MBP and PDGFαR) and neuronal distress and/or damage (GABA synthesis enzymes, GAD65 and GAD67, NGF, BDNF and related receptors), in two CNS areas, i.e. spinal cord and cerebellum, which are respectively severely and mildly affected by inflammation and demyelination. Tissues were sampled during acute, relapse/remission and chronic phases and results were analysed by two-way ANOVA.     

Heterogeneous nucleation mechanisms and formation of metastable phase assemblages induced by different crystalline seeds in a rapidly cooled andesitic melt

Pt-capsules loaded with a Pt-coil and two crystalline seeds immersed into an andesitic melt were rapidly cooled from 1300 to 1100 °C with a rate of 3 °C/min at atmospheric pressure and air oxygen fugacity. Results show that the Pt-coil does not induce any heterogeneous crystallization process as well as iron diffusion process from the melt into the platinum substrate. In contrast, the presence of crystalline seeds in a solidifying andesitic melt significantly alters the phase assemblage, composition and texture of the new-forming crystals in response to a heterogeneous nucleation mechanism and the formation of metastable phases.     

Charge transfer in model bioinspired carotene-porphyrin dyads

We present a computational study based on accurate DFT and TD-DFT methods on model bioinspired donor-acceptor dyads, formed by a carotenoid covalently linked to a tetraphenylporphyrin (TPP) at the ortho position of one of the TPP phenyl rings. Dyadic systems can be used in the construction of organic solar cells and development of efficient photocatalytic systems for the solar energy conversion, due to the unique advantages they offer in terms of synthetic feasibility. This study aims to describe the influence of chemical modifications on the absorption spectra, in particular on the lowest energy charge transfer bands. Effects of different metals of biological interest, i.e., Mg, Fe, Ni, and Zn, and of H(2)O and histidine molecules coordinated to the metals in different axial positions are rationalized.