Polycyclic aromatic hydrocarbons in the atmosphere: monitoring, sources, sinks and fate. II: Sinks and fate

This paper reviews the transformation processes that polycyclic aromatic hydrocarbons (PAHs) undergo in the atmosphere. These processes can take place both in the gas phase and in the particulate/aerosol one. Among the gas-phase processes, the most important ones are the daytime reaction with *OH and the nighttime reaction with *NO3. The relative importance of the two processes depends on the particular PAH molecule. For instance, gaseous naphthalene is mainly removed from the atmosphere upon reaction with *OH, while gaseous phenanthrene is mainly removed by reaction with *NO3. Oxy-, hydroxy-, and nitro-PAHs are the main transformation intermediates. Reaction with ozone and photolysis play a secondary role in the transformation of gaseous PAHs. The particle-associated processes are usually slower than the gas-phase ones, thus the gas-phase PAHs usually have shorter atmospheric lifetimes than those found on particulate. Due to the higher residence time on particulate when compared with the gas phase, direct or assisted photolysis plays a relevant role in the transformation of particle-associated PAHs. Among the other processes taking place in the condensed phase, nitration plays a very important role due to the health impact of nitro-PAHs, some of them being the most powerful mutagens found so far in atmospheric particulate extracts.     

Geminate rebinding in R-state hemoglobin: kinetic and computational evidence for multiple hydrophobic pockets

Biphasic geminate rebinding of CO to myoglobin upon flash photolysis has been associated to ligand distribution in hydrophobic cavities, structurally detected by time-resolved crystallography, xenon occupancy, and molecular simulations. We show that the time course of CO rebinding to human hemoglobin also exhibits a biphasic geminate rebinding when the protein is entrapped in wet nanoporous silica gel. A simple branched kinetic scheme, involving the bound state A, the primary docking site C, and a secondary binding site B was used to calculate the microscopic rates and the time-dependent population of the intermediate species. The activation enthalpies of the associated transitions were determined in the absence and presence of 80% glycerol. Potential hydrophobic docking cavities within the alpha and beta chains of hemoglobin were identified by computational modeling using xenon as a probe. A hydrophobic pocket on the distal side of the heme, corresponding to Xe4 in Mb, and a nearby site that does not have a correspondence in Mb were detected. Neither potential xenon sites on the proximal side nor a migration channel from the distal to proximal site was located. The small enthalpic barriers between states B and C are in very good agreement with the location of the xenon sites on the distal side. Furthermore, the connection between the two xenon sites is relatively open, explaining why the decreased mobility of the protein with viscosity only slightly perturbs the energetics of ligand migration between the two sites.     

Flexible polyfluorinated bis-diazirines as molecular adhesives

Motivated by a desire to develop flexible covalent adhesives that afford some of the same malleability in the adhesive layer as traditional polymer-based adhesives, we designed and synthesized two flexible, highly fluorinated bis-diazirines. Both molecules are shown to function as effective crosslinkers for polymer materials, and to act as strong adhesives when painted between two polymer objects of low surface energy, prior to thermal activation. Data obtained from lap-shear experiments suggests that greater molecular flexibility is correlated with improved mechanical compliance in the adhesive layer.

Flexible, highly fluorinated covalent adhesives are synthesized, and are shown to afford comparable C–H insertion efficiency and adhesion strength relative to a rigid analogue, while providing improved mechanical compliance in the adhesion layer.     

Unexpected and expeditious entry into trifluoromethyl aziridines from substituted beta-dicarbonyl compounds

[Reaction: see text]. One-pot aziridinations were obtained starting from substituted 2,2,2-trifluoroethyl beta-dicarbonyl compounds with nosyloxycarbamates in the presence of an excess of CaO as base. The unexpected ring closure reaction takes place at room temperature, leading to the N-protected alpha-trifluoromethyl aziridines with good yields. The reaction pathway seems to be influenced by the choice of the base.     

Synthesis and physico-chemical characterization of coordination compounds of 3d metals with potassium bicyclo[2.2.1]-hept-5-en-endo-2-oyl-hydroxylamine-3-carboxylate

Summary The ligand, potassium bicyclo[2.2.1]-hept-5-en-endo-2-oyl-hydroxylamine-3-carboxylate-monohydrate, KHL·H₂O₂ and its M(HL)₂ complexes, [{Fe(HL)₂}₂SO₄], K[FeL₂] and K₂[ML₂] (M=Mn^II, Fe^II, Co^II, Ni^II, Cu^II and Zn^II) were prepared and characterized. For all, except the sulphate complex of iron(III), a monomeric octahedral configuration was postulated and this is realized through the coordination of oxygen atoms of the carboxylic, carbonyl and oxime group of two mono-or di-anion ligands. The dianionic form of the ligand is the result of deprotonation of the carboxylic group and mide-alcohol form of the hydroxamic group. For the sulphate-containing iron(III) complex a dimeric coordination is proposed with two monoanions of the organic ligand (the carbonyl oxygens are not coordinated) and the bridging SO₄ group. The relative degree of covalency of the metal-carboxylic oxygen bond is 10.6–45.2% and increases in the order: Mn^IIIIIIIIIIIII. The complexes have been characterized by elemental and t.g. analysis and i.r. spectra.     

Analytical and Numerical Treatment of Continuous Ageing in the Voter Model

The conventional voter model is modified so that an agent’s switching rate depends on the ‘age’ of the agent—that is, the time since the agent last switched opinion. In contrast to previous work, age is continuous in the present model. We show how the resulting individual-based system with non-Markovian dynamics and concentration-dependent rates can be handled both computationally and analytically. The thinning algorithm of Lewis and Shedler can be modified in order to provide an efficient simulation method. Analytically, we demonstrate how the asymptotic approach to an absorbing state (consensus) can be deduced. We discuss three special cases of the age-dependent switching rate: one in which the concentration of voters can be approximated by a fractional differential equation, another for which the approach to consensus is exponential in time, and a third case in which the system reaches a frozen state instead of consensus. Finally, we include the effects of a spontaneous change of opinion, i.e., we study a noisy voter model with continuous ageing. We demonstrate that this can give rise to a continuous transition between coexistence and consensus phases. We also show how the stationary probability distribution can be approximated, despite the fact that the system cannot be described by a conventional master equation.     

Rapid Classification and Recognition Method of the Species and Chemotypes of Essential Oils by ATR-FTIR Spectroscopy Coupled with Chemometrics

In the present work, the applicability of attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy, coupled with chemometric tools in recognizing essential oils (EOs) for routine control, was evaluated. EOs belonging to Mentha, Cymbopogon, and Lavandula families and to S. rosmarinus and T. vulgaris species were analyzed, and the performance of several untargeted approaches, based on the synergistic combination of ATR-FTIR and Partial Least Squares Discriminant Analysis (PLS-DA), was tested to classify the species and chemotypes. Different spectra pre-processing methods were employed, and the robustness of the built models was tested by means of a Receiver Operating Characteristic (ROC) curve and random permutations test. The application of these approaches revealed fruitful results in terms of sensitivity and specificity, highlighting the potentiality of ATR-FTIR and chemometrics techniques to be used as a sensitive, cost-effective, and rapid tool to differentiate EO samples according to their species and chemotype.     

Phytochemical Characterization,Anti-Oxidant,Anti-Enzymatic and Cytotoxic Effects of Artemisia verlotiorum Lamotte Extracts: A New Source of Bioactive Agents

Artemisia verlotiorum Lamotte is recognized medicinally given its long-standing ethnopharmacological uses in different parts of the world. Nonetheless, the pharmacological properties of the leaves of the plant have been poorly studied by the scientific community. Hence, this study aimed to decipher the phytochemicals; quantify through HPLC-ESI-MS analysis the plant’s biosynthesis; and evaluate the antioxidant, anti-tyrosinase, amylase, glucosidase, cholinesterase, and cytotoxicity potential on normal (NIH 3T3) and human liver and human colon cancer (HepG2 and HT 29) cell lines of this plant species. The aqueous extract contained the highest content of phenolics and phenolic acid, methanol extracted the most flavonoid, and the most flavonol was extracted by ethyl acetate. The one-way ANOVA results demonstrated that all results obtained were statistically significant at p < 0.05. A total of 25 phytoconstituents were identified from the different extracts, with phenolic acids and flavonoids being the main metabolites. The highest antioxidant potential was recorded for the aqueous extract. The best anti-tyrosinase extract was the methanolic extract. The ethyl acetate extract of A. verlotiorum had the highest flavonol content and hence was most active against the cholinesterase enzymes. The ethyl acetate extract was the best α-glucosidase and α-amylase inhibitor. The samples of Artemisia verlotiorum Lamotte in both aqueous and methanolic extracts were found to be non-toxic after 48 h against NIH 3T3 cells. In HepG2 cells, the methanolic extract was nontoxic up to 125 µg/mL, and an IC₅₀ value of 722.39 µg/mL was recorded. The IC₅₀ value exhibited in methanolic extraction of A. verlotiorum was 792.91 µg/mL in HT29 cells. Methanolic extraction is capable of inducing cell cytotoxicity in human hepatocellular carcinoma without damaging normal cells. Hence, A. verlotiorum can be recommended for further evaluation of its phytochemical and medicinal properties.     

Production of Mesoglycan/PCL Based Composites through Supercritical Impregnation

The development of targeted therapies for wound repair is knowing a growing interest due to the increasing aging of the population and the incidence of chronic pathologies, mainly pressure ulcers. Among molecules recruiting cell populations and promoting the formation of new vital tissue, sodium mesoglycan (MSG) has been proven to be effective in wound healing. In this work, MSG impregnation of polymer matrices has been attempted by a supercritical carbon dioxide-based process. Polymeric matrices are composed of polycaprolactone blends, where water-soluble polymers, polyethylene glycol, polyvinyl pyrrolidone, gelatin, and thermoplastic starch, have been employed to modulate the MSG release, making the devices potentially suitable for topical administrations. Two different techniques have been used to obtain the films: the first one is compression molding, producing compact and continuous structures, and the second one is electrospinning, producing membrane-like designs. A higher amount of MSG can be loaded into the polymeric matrix in the membrane-like structures since, in these films, the impregnation process is faster than in the case of compression molded films, where the carbon dioxide has firstly diffused and then released the active molecule. The type of water-soluble polymer influences the drug release rate: the blend polycaprolactone-gelatin gives a prolonged release potentially suitable for topical administration.     

Advances in Hybrid Composites for Photocatalytic Applications: A Review

Heterogeneous photocatalysts have garnered extensive attention as a sustainable way for environmental remediation and energy storage process. Water splitting, solar energy conversion, and pollutant degradation are examples of nowadays applications where semiconductor-based photocatalysts represent a potentially disruptive technology. The exploitation of solar radiation for photocatalysis could generate a strong impact by decreasing the energy demand and simultaneously mitigating the impact of anthropogenic pollutants. However, most of the actual photocatalysts work only on energy radiation in the Near-UV region (<400 nm), and the studies and development of new photocatalysts with high efficiency in the visible range of the spectrum are required. In this regard, hybrid organic/inorganic photocatalysts have emerged as highly potential materials to drastically improve visible photocatalytic efficiency. In this review, we will analyze the state-of-art and the developments of hybrid photocatalysts for energy storage and energy conversion process as well as their application in pollutant degradation and water treatments.