Diplomatic Villa

Zadaním práce je návrh rezidencie pre diplomatické účely. Stavba sa nachádza v lokalite Troja, ktorá bola spracovaná v súčasne v ateliéri.The assignment was to design a residence with diplomatic purpose. Building is located in Troja, which was elaborated in studio

The Importance of Participation in Regeneration of Peripheral Urban Spaces: the Experience of “Serpentone Reload”

Suburbs are often very contradictory places. Despite great part of urban population live there, these parts of cities are mostly considered as degradation places. The topic of suburbs regeneration is relevant today. Nevertheless, often expensive interventions implemented by local authorities fail to regenerate their public spaces, increasing the degradation condition. This paper presents the experience of “Serpentone reload”, a workshop based on participatory reactivation of abandoned or underused spaces and buildings in "Cocuzzo/Serpentone" neighbourhood in Potenza (Basilicata, Italy). The workshop particularly focused on the reuse of the "Ship", an underground building with a park coverage completed in 2010 and designed by the firm Archea. The "Ship" has been forgotten and not used for long time, not only by the neighbourhood, but by the whole citizenship, because it has been perceived as an extraneous element and the result of an imposition from the top, definitely not the outcome of shared choices. During the workshop, the "Ship" (“Nave” in Italian language) has become an art centre called N.Av.E. (New Expressive Adventures – Nuove Avventure Espressive in Italian), a place capable to host temporary events (expositions, lectures, theatre and dance performance, movies projection, etc.). Such a choice has allowed the neighbourhood and the city to take back that “object” so hated as ignored. The experience is particularly significant, because it shows how low cost interventions, realized with citizens involvement and participation, could contribute to the regeneration of peripheral urban areas more than expensive and complex imposed interventions, which often do not take into account dwellers real needs and expectations

Unique Reaction Path in Heterogeneous Catalysis: The Concerted Semi-Hydrogenation of Propyne to Propene on CeO2

ABSTRACT: Despite its ubiquity in homogeneous and enzymatic catalysis, concerted mechanisms have been over- looked for heterogeneously catalyzed reactions. The elusive nature of transition states leaves Density Functional Theory, DFT, as the only robust tool for their identification and characterization. By means of this method, we show that a concerted path takes part in the recently discovered semi- hydrogenation of propyne on CeO2, for which an excellent activity and selectivity have been reported. The high surface H coverage imposed by the experimental hydrogenation con- ditions induces site isolation and drives the reaction through a six-membered ring transition state. This unprecedented pathway accounts for many of the experimental observations, such as the unique syn-stereoselectivity, the excellent alkene selectivities, or the high temperature and large H2/alkyne ratios required

When the Solvent Locks the Cage: Theoretical Insight into the Transmetalation of MOF‐5 Lattices and Its Kinetic Limitations

Transmetalation is an innovative postsynthetic strategy for tailoring the properties of metal−organic frameworks (MOFs), allowing stable unprecedented metal coordination environments. Although the experimental synthetic protocol is well- established, the underlying mechanism for transmetalation is still unknown. In this work, we propose two different solvent-mediated reaction paths for the Ni transmetalation in Zn- MOF-5 lattices through density functional theory simulations. In both mechanisms, the bond strength between the exchanged metal and the solvent is the key descriptor that controls the degree of transmetalation. We also show that the role of the solvent in this process is twofold: it initially promotes Zn exchange, but if the metal−solvent bond is too strong, it blocks the second transmetalation cycle by restricting the lattice flexibility. The competition between these two effects leads the degree of incorporation of metal into MOF-5 to display a volcano-type dependence with respect to the metal−solvent bond strength for different transition metal ions

DNA barcoding as a complementary tool for conservation and valorisation of forest resources

Since the pre-historic era, humans have been using forests as a food, drugs and handcraft reservoir. Today, the use of botanical raw material to produce pharmaceuticals, herbal remedies, teas, spirits, cosmetics, sweets, dietary supplements, special industrial compounds and crude materials constitute an important global resource in terms of healthcare and economy. In recent years, DNA barcoding has been suggested as a useful molecular technique to complement traditional taxonomic expertise for fast species identification and biodiversity inventories. In this study, in situ application of DNA barcodes was tested on a selected group of forest tree species with the aim of contributing to the identification, conservation and trade control of these valuable plant resources.The “core barcode” for land plants (rbcL, matK, and trnH-psbA) was tested on 68 tree specimens (24 taxa). Universality of the method, ease of data retrieval and correct species assignment using sequence character states, presence of DNA barcoding gaps and GenBank discrimination assessment were evaluated. The markers showed different prospects of reliable applicability. RbcL and trnH-psbA displayed 100% amplification and sequencing success, while matK did not amplify in some plant groups. The majority of species had a single haplotype. The trnH-psbA region showed the highest genetic variability, but in most cases the high intra-specific sequence divergence revealed the absence of a clear DNA barcoding gap. We also faced an important limitation because the taxonomic coverage of the public reference database is incomplete. Overall, species identification success was 66.7%.This work illustrates current limitations in the applicability of DNA barcoding to taxonomic forest surveys. These difficulties urge for an improvement of technical protocols and an increase of the number of sequences and taxa in public databases

Diversity at the Water–Metal Interface: Metal, Water Thickness, and Confinement Effects

The structure and properties of water films in contact with metal surfaces are crucial to understand the chemical and electrochemical processes involved in energy-related technologies. The nature of thin water films on Pd, Pt, and Ru has been investigated by first-principles molecular dynamics to assess how the chemistry at the water–metal surface is responsible for the diversity in the behavior of the water layers closer to the metal. The characteristics of liquid water: the radial distribution functions, coordination, and fragment speciation appear only for unconfined water layers of a minimum of 1.4 nm thick. In addition, the water layer is denser in the region closest to the metal for Pd and Pt, where seven- and five-membered ring motifs appear. These patterns are identical to those identified by scanning tunneling microscopy for isolated water bilayers. On Ru densification at the interface is not observed, water dissociates, and protons and hydroxyl groups are locked at the surface. Therefore, the acid–base properties in the area close to the metal are not perturbed, in agreement with experiments, and the bulk water resembles an electric double layer. Confinement affects water making it closer to ice for both structural and dynamic properties, thus being responsible for the higher viscosity experimentally found at the nanoscale. All these contributions modify the solvation of reactants and products at the water–metal interface and will affect the catalytic and electrocatalytic properties of the surface

Dynamic DMF Binding in MOF-5 Enables the Formation of Metastable Cobalt-Substituted MOF-5 Analogues

Multinuclear solid-state nuclear magnetic resonance, mass spectrometry, first-principles molecular dynamics simulations, and other complementary evidence reveal that the coordination environment around the Zn2+ ions in MOF-5, one of the most iconic materials among metal–organic frameworks (MOFs), is not rigid. The Zn2+ ions bind solvent molecules, thereby increasing their coordination number, and dynamically dissociate from the framework itself. On average, one ion in each cluster has at least one coordinated N,N-dimethylformamide (DMF) molecule, such that the formula of as-synthesized MOF-5 is defined as Zn4O(BDC)3(DMF)x (x = 1–2). Understanding the dynamic behavior of MOF-5 leads to a rational low-temperature cation exchange approach for the synthesis of metastable Zn4–xCoxO(terephthalate)3 (x > 1) materials, which have not been accessible through typical high-temperature solvothermal routes thus far.National Science Foundation (U.S.) (NSF CAREER Award (DMR-1452612))National Science Foundation (U.S.) (NSF Graduate Research Fellowship Grant 1122374)National Institutes of Health (U.S.) (grant EB002026)Natural Sciences and Engineering Research Council of CanadaGovernment of Canada (Banting postdoctoral fellowship

Structure, Activity, and Deactivation Mechanisms in Double Metal Cyanide Catalysts for the Production of Polyols

Polyether polyols are used widely in the plastic and coating in- dustries in the form of polyurethanes. The polymerization of epoxides can be catalyzed by double metal cyanides (DMCs), Zn3[Co(CN)6]2. These catalysts were first reported in the 1960s by General Tire Inc. and provide products with excellent tech- nical features, which are better than those that result from tra- ditional alkaline polymerization as side reactions are alleviated. However, DMC-catalyzed polymerization is not free of draw- backs as high-molecular-weight side products (1–3 wt %) can form in the propylene process. These tails are detrimental to the subsequent use of these polymers, in particular to foam stability. Despite the wide industrial interest in DMCs, there are only a few experimental studies and a complete lack of theo- retical research of their structure, activity, and performance. The present work is thus the first attempt to describe the nature of the active site, the main polymerization mechanism, and two potential origins for the high-weight tails from a theo- retical standpoint by analyzing three crucial steps in the poly- merization process