Oxoiron(V) Complexes of Relevance in Oxidation Catalysis of Organic Substrates

The selective oxidation of alkane and olefin moieties are reactions of fundamental importance in both chemical synthesis and biology. Nature efficiently catalyzes the oxidation of hydrocarbons using iron-dependent enzymes, which operate through the mediation of oxoiron(IV) or oxoiron(V) species. In the quest for chemo, regio and stereoselective transformations akin to those taking place in nature, bioinspired iron catalysts have been developed and understanding their mechanism of action has become a particularly relevant area of research. While a prominent advance in the preparation and characterization of oxoiron(IV) species has been accomplished, oxoiron(V) species remain exceedingly rare, presumably because the high reactivity that makes them particularly interesting also makes them difficult to observe. This review summarizes the advances in the field, focusing in synthetic systems for which the oxoiron(V) species relevant in these transformations have been directly detected and spetroscopically characterized.     

Equilibria,kinetics and mechanism for the degradation of the cytotoxic compound L-NG-nitroarginine

L-N^G-nitroarginine (LNNA), an analog of L-arginine, is a competitive inhibitor of nitric oxide synthase which causes the selective reduction of blood flow to tumor cells. Despite the potential of LNNA to function as an adjuvant in cancer therapies, its poor solubility and stability have hindered the development of an injectable formulation of LNNA that is suitable for human administration. This work, for the first time, details a systematic study on the determination of equilibrium K_a constants and the rate law of LNNA degradation. The four K_a values of LNNA were determined to be 1.03, 1.10?×?10^?2, 2.51?×?10^?10, and 1.33?×?10^?13 M. From the kinetic and equilibrium studies, we have shown that the deprotonated form of LNNA is the main form of LNNA that undergoes degradation in aqueous media at room temperature. The rate law of LNNA degradation was found to be first order with respect to OH^? concentration and first order with respect to LNNA^? concentration. The rate constant at 25?°C and 1?atm was determined to be 0.04453 M^?1min^?1. A base catalyzed mechanism of LNNA degradation was proposed based on the kinetic study. The mechanism was found to be very useful in explaining the discrepancies and changes of the rate law at different pH values. It is thus recommended that LNNA should be formulated as a concentrated solution in acidic conditions for maximum chemical stability during storage and be diluted with a basic solution to near physiological pH just before administration.     

Ionic‐Liquid Gating of InAs Nanowire‐Based Field‐Effect Transistors

Here, the operation of a field‐effect transistor based on a single InAs nanowire gated by an ionic liquid is reported. Liquid gating yields very efficient carrier modulation with a transconductance value 30 times larger than standard back gating with the SiO₂/Si₊₊ substrate. Thanks to this wide modulation, the controlled evolution from semiconductor to metallic‐like behavior in the nanowire is shown. This work provides the first systematic study of ionic‐liquid gating in electronic devices based on individual III–V semiconductor nanowires: this architecture opens the way to a wide range of fundamental and applied studies from the phase transitions to bioelectronics.     

Self‐Assembly of Atomically Thin Chiral Copper Heterostructures Templated by Black Phosphorus

The fabrication of 2D systems for electronic devices is not straightforward, with top‐down low‐yield methods often employed leading to irregular nanostructures and lower quality devices. Here, a simple and reproducible method to trigger self‐assembly of arrays of high aspect‐ratio chiral copper heterostructures templated by the structural anisotropy in black phosphorus (BP) nanosheets is presented. Using quantitative atomic resolution aberration‐corrected scanning transmission electron microscopy imaging, in situ heating transmission electron microscopy and electron energy‐loss spectroscopy arrays of heterostructures forming at speeds exceeding 100 nm s^?1 and displaying long‐range order over micrometers are observed. The controlled instigation of the self‐assembly of the Cu heterostructures embedded in BP is achieved using conventional electron beam lithography combined with site specific placement of Cu nanoparticles. Density functional theory calculations are used to investigate the atomic structure and suggest a metallic nature of the Cu heterostructures grown in BP. The findings of this new hybrid material with unique dimensionality, chirality, and metallic nature and its triggered self‐assembly open new and exciting opportunities for next generation, self‐assembling devices.     

Double perovskite Cs2AgBiBr6 radiation sensor: synthesis and characterization of single crystals

Journal of Materials Science - Single crystals of lead-free halide double perovskite Cs2AgBiBr6 sensor material manifest a remarkable potential for application in radiation detection and imaging....     

Interaction and Outcomes in Collaborative Storytelling Systems: a Framework,a Field Study,and a Model

In the last decades, advances in interactive information technologies have facilitated collaborative fiction writing, which has become widespread and large-scale. This paper proposes a framework to analyze collaborative storytelling systems, made of a set of parameters divided into six conceptual areas. Four of them relate to the systems and two (process and output) to the results of the collaboration. Through this framework we can study more precisely these different factors of the systems, their interplay, and how they impact the creators’ performance. We also present a controlled extended-duration field study on collaborative storytelling, and we use this framework to comparatively analyze these observations and other relevant experiences in the field of co-creation of shared narrative spaces. As a result, we propose a human-information interaction model for collaborative narrative systems, intended to better support co-creation and address the barriers of this kind of systems turning them into new opportunities for collaboration.     

Stabilization of the Reductase Domain in the Catalytically Self‐Sufficient Cytochrome P450BM3 by Consensus‐Guided Mutagenesis

The multidomain, catalytically self‐sufficient cytochrome P450 BM‐3 from Bacillus megaterium (P450_BM3) constitutes a versatile enzyme for the oxyfunctionalization of organic molecules and natural products. However, the limited stability of the diflavin reductase domain limits the utility of this enzyme for synthetic applications. In this work, a consensus‐guided mutagenesis approach was applied to enhance the thermal stability of the reductase domain of P450_BM3. Upon phylogenetic analysis of a set of distantly related P450s (>38 % identity), a total of 14 amino acid substitutions were identified and evaluated in terms of their stabilizing effects relative to the wild‐type reductase domain. Recombination of the six most stabilizing mutations generated two thermostable variants featuring up to tenfold longer half‐lives at 50 °C and increased catalytic performance at elevated temperatures. Further characterization of the engineered P450_BM3 variants indicated that the introduced mutations increased the thermal stability of the FAD‐binding domain and that the optimal temperature (T_opt) of the enzyme had shifted from 25 to 40 °C. This work demonstrates the effectiveness of consensus mutagenesis for enhancing the stability of the reductase component of a multidomain P450. The stabilized P450_BM3 variants developed here could potentially provide more robust scaffolds for the engineering of oxidation biocatalysts.     

Ceria‐coated diesel particulate filters for continuous regeneration

The potential of diesel particulate filters wash‐coated with highly dispersed nano‐metric ceria particles for continuous regeneration has been investigated. To this end, catalytic filters were prepared, soot‐loaded (avoiding the formation of the cake layer), and regenerated—under isothermal conditions—at temperature ranging from 200–600°C. Results have shown that catalytic oxidation of soot starts from 300°C and, at all temperatures, the selectivity to CO₂ is higher than 99%. 475°C is the minimum temperature at which the filter is regenerated via catalytic path. At this temperature, the catalytic filter maintains substantially the same performance over repeated cycles of soot loading and regeneration, indicating that the thermal stability of ceria is preserved. This has been further confirmed by comparison between the outcomes obtained from characterization (X‐ray powder diffraction, N₂ adsorption at 77 K, Hg intrusion porosimetry, and scanning electron microscope/energy dispersive X‐ray analysis) of fresh filter and filter subjected to repeated regeneration tests. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3442–3449, 2017     

Institutionalizing EU strategic spatial planning into domestic planning systems: trajectories of change in Italy and England

ABSTRACT

This paper proposes approaching the emergence and evolution of the Europeanization of national planning using conceptual frameworks from historical institutionalism in order to shed light on the mechanisms and trajectories of domestic change arising from the influence of EU strategic planning. It seeks in particular to examine Europeanization in terms of the extent to which EU spatial planning has become a driving force for institutional changes in very different national planning systems. Returning to the changes that occurred in the Italian and English planning systems in the last two decades, the author provides insight into the attempts to insert and transpose EU spatial planning concepts and instruments into domestic systems, dealing with path dependency and European influence. By reading these processes from a historical institutionalist perspective, the paper aims to enhance understanding of the relative influence of European spatial planning on national planning systems, identifying mechanisms and trajectories of domestic change in different planning systems. Key findings concern the diverse modes and degree of institutionalization of EU strategic spatial planning, examining tendencies to replace the status quo through displacements in England and to progress through a path-dependent trajectory in Italy.     

Exposure to urban stressor and effects on free testosterone in female workers

BACKGROUND: The aim of the study is to evaluate if occupational exposure to chemical, physical and psycho-social urban stressor could cause alterations in plasma free testosterone (T) levels and related diseases in female traffic police vs. control group. PATIENTS AND METHODS: The research was carried out on initial sample of 468 female Municipal Police employees (209 traffic police and 259 controls). After excluding the principal confounding factors, traffic police were matched with controls by age, working life, menstrual cycle day, BMI, drinking habit, cigarette smoking habit, liquorice and soy intake in diet, habitual consumption of Italian coffee. There were 96 female traffic police and 96 controls included in the study. RESULTS: T mean levels were significantly higher in female traffic police compared to controls (p=0.000). The distribution of T values in traffic police and in controls was significant (p=0.000). No significant differences were found comparing the percentage in traffic police and controls concerning dystocial, premature and post-term birth. An increase in mental health disorders was found in traffic police compared to controls but the difference was not significant. CONCLUSION: The increase in T plasma levels observed in traffic police vs. controls can be due to a chronic working exposure to low doses of environmental chemical urban stressor. According to our previous researches T could be used as an early biological marker even before the onset of the related disorders.