Poly(hydroxyalkanoates)-Based Polymeric Nanoparticles for Drug Delivery

Poly (hydroxyalkanoates) (PHAs) have recently attracted a great deal of academic and industrial interest for their biodegradability and biocompatibility making them suitable for environmental and biomedical applications. Poly(3-hydroxybutyrate-) (PHB-) and Poly(DL-lactide-co-glycolide) (PLGA-) based nanoparticles were prepared using the dialysis method as yet unreported for the preparation of nanoparticles based on PHB. Processing conditions were varied in order to evaluate their influence on morphology, drug encapsulation, and size of nanoparticles. The relevant results obtained give a theoretical understanding of the phenomenon occurring during colloidal formation. The adopted procedure allows for a relatively small diameter and homogeneity in size distribution of the PHB nanoparticles to be obtained compared to other methods like the one based on solvent evaporation which leads to particles on microscale. The biocompatibility of PHB and relative nanoparticles was investigated and both exhibited very good cytocompatibility

granitoid magmas preserved as melt inclusions in high grade metamorphic rock

This review presents a compositional database of primary anatectic granitoid magmas, entirely based on melt inclusions (MI) in high-grade metamorphic rocks. Although MI are well known to igneous petrologists and have been extensively studied in intrusive and extrusive rocks, MI in crustal rocks that have undergone anatexis (migmatites and granulites) are a novel subject of research. They are generally trapped along the heating path by peritectic phases produced by incongruent melting reactions. Primary MI in high-grade metamorphic rocks are small, commonly 5–10 μm in diameter, and their most common mineral host is peritectic garnet. In most cases inclusions have crystallized into a cryptocrystalline aggregate and contain a granitoid phase assemblage (nanogranitoid inclusions) with quartz, K-feldspar, plagioclase, and one or two mica depending on the particular circumstances. After their experimental remelting under high-confining pressure, nanogranitoid MI can be analyzed combining several techniques (EMP, LA-ICP-MS, NanoSIMS, Raman). The trapped melt is granitic and metaluminous to peraluminous, and sometimes granodioritic, tonalitic, and trondhjemitic in composition, in agreement with the different ![Formula][1] conditions of melting and protolith composition, and overlap the composition of experimental glasses produced at similar conditions. Being trapped along the up-temperature trajectory—as opposed to classic MI in igneous rocks formed during down-temperature magma crystallization—fundamental information provided by nanogranitoid MI is the pristine composition of the natural primary anatectic melt for the specific rock under investigation. So far ~600 nanogranitoid MI, coming from several occurrences from different geologic and geodynamic settings and ages, have been characterized. Although the compiled MI database should be expanded to other potential sources of crustal magmas, MI data collected so far can be already used as natural "starting-point" compositions to track the processes involved in formation and evolution of granitoid magmas. [1]: /embed/mml-math-1.gi

Primary crustal melt compositions: Insights into the controls, mechanisms and timing of generation from kinetics experiments and melt inclusions

We explore the controls, mechanisms and timing of generation of primary melts and their compositions, and show that the novel studies of melt inclusions in migmatites can provide important insights into the processes of crustal anatexis of a particular rock. Partial melting in the source region of granites is dependent on five main processes: (i) supply of heat; (ii) mineral–melt interface reactions associated with the detachment and supply of mineral components to the melt, (iii) diffusion in the melt, (iv) diffusion in minerals, and (v) recrystallization of minerals. As the kinetics of these several processes vary over several orders of magnitude, it is essential to evaluate in Nature which of these processes control the rate of melting, the composition of melts, and the extent to which residue–melt chemical equilibrium is attained under different circumstances. To shed light on these issues, we combine data from experimental and melt inclusion studies. First, data from an extensive experimental program on the kinetics of melting of crustal protoliths and diffusion in granite melt are used to set up the necessary framework that describes how primary melt compositions are established during crustal anatexis. Then, we use this reference frame and compare compositional trends from experiments with the composition of melt inclusions analyzed in particular migmatites. We show that, for the case of El Hoyazo anatectic enclaves in lavas, the composition of glassy melt inclusions provides important information on the nature and mechanisms of anatexis during the prograde suprasolidus history of these rocks, including melting temperatures and reactions, and extent of melt interconnection, melt homogenization and melt–residue equilibrium. Compositional trends in several of the rehomogenized melt inclusions in garnet from migmatites/granulites in anatectic terranes are consistent with diffusion in melt-controlled melting, though trace element compositions of melt inclusions and coexisting minerals are necessary to provide further clues on the nature of anatexis in these particular rocks.This work was supported by the National Science Foundation [grants EAR-9603199, EAR-9618867, EAR-9625517 and EAR-9404658], the Italian Consiglio Nazionale delle Ricerche, the European Commission (grant 01-LECEMA22F through contract No. ERAS-CT-2003-980409; and a H2020 Marie Skłodowska-Curie Actions under grant agreement No. 654606), the Italian Ministry of Education, University and Research (grants PRIN 2007278A22, 2010TT22SC and SIR RBSI14Y7PF), the Università degli Studi di Padova [Progetto di Ateneo CPDA107188/10 and a Piscopia—Marie Curie Fellowship under grant agreement No. 600376], the Australian Research Council (Australian Professorial Fellowship and Discovery Grants Nos. DP0342473 and DP0556700), and the National Research Foundation (South Africa; Incentives For Rated Researchers Program)

I was not born cubic, said low-temperature metamorphic garnet

Garnet is the paradigmatic cubic mineral of metamorphic and igneous rocks, and is generally regarded as optically isotropic. Nonetheless, evident birefringence is observed, particularly in the rare Ca-Fe3+ hydrogarnets, which is attributed to the coexistence of two or more cubic phases. A weak birefringence, with rare examples of optical sector zoning, has also been documented in much more common Fe2+-Mg-Mn garnets, but an adequate explanation for its cause is, so far, lacking. Here we show that optically anisotropic garnets are much more widespread than previously thought, both in blueschists and blueschist-facies rocks, as well as in lower greenschist-facies phyllites, but they are frequently overlooked when working with conventional, 30-µm-thick thin sections. Utilizing a multi-technique approach including optical microstructural analysis, BSEM, EMPA, EBSD, FTIR, TEM, EDT and single-crystal XRD, we demonstrate here that the birefringence in these garnets is related to their tetragonal symmetry, that it is not due to strain, and that crystals are twinned according to a merohedral law. We also show that the birefringent garnets from blueschists and phyllites are anhydrous, lacking any hydrogarnet component, and have compositions dominated by almandine (58-79%) and grossular (19-30%) with variable spessartine (0-21%) and very low pyrope (1-7%). Considering the widespread occurrence of optically anisotropic OH-free garnets in blueschists and phyllites, their common low-grade metamorphic origin, and the occurrence of optically isotropic garnets with similar Ca-rich almandine composition in higher-grade rocks, we conclude that garnet does not grow with cubic symmetry in low-temperature rocks (< 400 ◦C). The tetragonal structure appears to be typical of Fe-Ca-rich compositions, with very low Mg contents. Cubic but optically sector-zoned garnet in a lower amphibolite-facies metapelite from the eastern Alps suggests that preservation of tetragonal garnet is favored in rocks which did not progress to T> ≈500 ◦C, where transition to the cubic form, accompanied by change of stable chemical composition, would take place. Our data show that the crystal-chemistry of garnet, its thermodynamics and, in turn, its use in unravelling petrogenetic processes in cold metamorphic environments need to be re-assessed

Garnet, the archetypal cubic mineral, grows tetragonal

Garnet is the archetypal cubic mineral, occurring in a wide variety of rock types in Earth’s crust and upper mantle. Owing to its prevalence, durability and compositional diversity, garnet is used to investigate a broad range of geological processes. Although birefringence is a characteristic feature of rare Ca–Fe3+ garnet and Ca-rich hydrous garnet, the optical anisotropy that has occasionally been documented in common (that is, anhydrous Ca–Fe2+–Mg–Mn) garnet is generally attributed to internal strain of the cubic structure. Here we show that common garnet with a non-cubic (tetragonal) crystal structure is much more widespread than previously thought, occurring in low-temperature, high-pressure metamorphosed basalts (blueschists) from subduction zones and in low-grade metamorphosed mudstones (phyllites and schists) from orogenic belts. Indeed, a non-cubic symmetry appears to be typical of common garnet that forms at low temperatures (<450 °C), where it has a characteristic Fe–Ca-rich composition with very low Mg contents. We propose that, in most cases, garnet does not initially grow cubic. Our discovery indicates that the crystal chemistry and thermodynamic properties of garnet at low-temperature need to be re-assessed, with potential consequences for the application of garnet as an investigative tool in a broad range of geological environments

La catena di custodia del dato digitale: tra anelli solidi e anelli mancanti

Il contributo ricostruisce la disciplina italiana della catena di custodia dell'elemento di prova digitale evidenziandone punti di forza e fragilità

C–O–H fluid-melt-rock interaction in graphitic granulites and problems of quantifying carbon budget in the lower continental crust

Estimates on the geological carbon cycle are subject to large uncertainties that can be reduced by thorough observation of rocks. In this contribution, we focus specifically on C-O-H fluid-melt-rock interactions in graphitic metapelitic granulites and on their bearing to the carbon budget of granulitic roots of continents. We provide robust microstructural and thermometric constraints on the coexistence of anatectic silicate melts and C-O-H fluids up to near ultrahigh temperature conditions in the archetypal crustal section of Ivrea-Verbano Zone (IVZ, Italian Alps). Fluid inclusions in garnet are investigated before and after high-temperature experiments, and contain considerable proportions of CO2, CH4, N2, but lower H2O than predicted for graphitic systems at granulite facies. When comparing and contrasting the melt compositions obtained by Perple_X and rhyoliteMELTS with natural melts from IVZ, a much better match is obtained by the former, questioning the choice of rhyolite-MELTS for modelling melting equilibria of metasedimentary rocks and for quantifying carbon budget of the lower crust. Overall, data show that assuming only a limited extent of fluid-melt immiscibility in the deep crust contradicts the evidence from natural rocks and prompts to an incomplete view of actual carbon behavior and carbonic fluids. The available experimental dataset on CO2 solubility in felsic melts cannot be used to interpret the volatile budget of melt inclusions in graphitic migmatites and granulites, as most solubility experiments were conducted under carbonate-saturated (i.e. highly oxidizing) conditions which maximize CO2 content of melt, compared to graphitic (i.e. more reducing) protoliths. As a consequence, thermodynamic models still cannot account for all the complexities related with interactions among H2O-CO2-CH4 ternary fluids, H2Oand CO2-bearing anatectic melts and graphite-bearing residues in graphitic metapelites. Targeted experimental studies are therefore crucial to boost substantial computational efforts, before any precise estimates on carbon budget and fluxes in the lower anatectic crust can be made

High-temperature metamorphism and crustal melting: Working with melt inclusions

The application of melt inclusion (MI) studies to migmatitic and granulitic terranes is a recent, small-scale approach for a better understanding of melting in the continental crust. In order to show the role of anatectic MI in providing a wealth of microstructural and compositional information on high-temperature metamorphism and crustal anatexis, we review a series of studies on the crustal footwall of the Ronda peridotites (Betic Cordillera, S Spain), which consists of an inverted metamorphic sequence with granulite-facies rocks showing extensive melting on top and amphibolites-facies rocks at the bottom. We studied the microstructures and geochemistry of small (2-10 mu m) primary MI hosted in peritectic garnet of metatexites at the bottom of the migmatitic sequence and of mylonitic diatexites close to the contact with the mantle rocks. The occurrence of MI is a proof that the investigated rocks were partially melted at some time in their history, despite other microstructures indicating the former presence of melt in diatexites were erased by deformation. MI show a variable degree of crystallization ranging from totally glassy to fully crystallized (nanogranites), consisting of Qtz+Pl+Kfs+Bt+Ms aggregates (often modal Kfs > P1 in diatexites). Piston cylinder remelting experiments led to the complete rehomogenization of nanogranites in metatexites at the conditions inferred for anatexis. Compositions of investigated MI are all leucogranitic and peraluminous and differ from those of coexisting leucosomes and from melts calculated by phase equilibria modeling. Systematic compositional variations have been observed between ME in metatexites and diatexites: the former commonly show higher H2O, CaO, Na2O/K2O and lower FeO. The compositions of MI in metatexites and diatexites are interpreted to record the composition of the anatectic melts produced from a peraluminous greywacke i) on, and immediately after crossing, the fluid-saturated solidus of this metasedimentary rock, and ii) during anatexis via biotite dehydration melting at increasing temperature, respectively. While partial melting at the bottom of the migmatitic sequence likely started in the presence of an aqueous fluid phase, MI data support the fluid-absent character of the melting event in diatexites. Anatectic MI should therefore be considered as a new and important opportunity to understand the partial melting processes