Microfluidic fabrication of gadolinium-doped hydroxyapatite for theragnostic applications

Among the several possible uses of nanoparticulated systems in biomedicine, their potential as theragnostic agents has received significant interest in recent times. In this work, we have taken advantage of the medical applications of Gadolinium as a contrast agent with the versatility and huge array of possibilities that microfluidics can help to create doped Hydroxyapatite nanoparticles with magnetic properties in an efficient and functional way. First, with the help of Computational Fluid Dynamics (CFD), we performed a complete and precise study of all the elements and phases of our device to guarantee that our microfluidic system worked in the laminar regime and was not affected by the presence of nanoparticles through the flow requisite that is essential to guarantee homogeneous diffusion between the elements or phases in play. Then the obtained biomaterials were physiochemically characterized by means of XRD, FE-SEM, EDX, confocal Raman microscopy, and FT-IR, confirming the successful incorporation of the lanthanide element Gadolinium in part of the Ca (II) binding sites. Finally, the magnetic characterization confirmed the paramagnetic behaviour of the nanoparticles, demonstrating that, with a simple and automatized system, it is possible to obtain advanced nanomaterials that can offer a promising and innovative solution in theragnostic applications.M.S.: R.R. and J.M.R. thank Xunta de Galicia for support (ED431B 2022/36), R.R. is granted by the Program for the requalification, international mobility, and attraction of talent in the Spanish university system, modality Margarita Salas. J.M. and I.F.L. acknowledge support from the Spanish Agencia Estatal de Investigación (project PID2019-104296GB-I00), and I.F.L. from Xunta de Galicia (grant ED481A-2020/149)

Covalent C–N Bond Formation through a Surface Catalyzed Thermal Cyclodehydrogenation

The integration of substitutional dopants at predetermined positions along the hexagonal lattice of graphene-derived polycyclic aromatic hydrocarbons is a critical tool in the design of functional electronic materials. Here, we report the unusually mild thermally induced oxidative cyclodehydrogenation of dianthryl pyrazino[2,3-g]quinoxalines to form the four covalent C–N bonds in tetraazateranthene on Au(111) and Ag(111) surfaces. Bond-resolved scanning probe microscopy, differential conductance spectroscopy, along with first-principles calculations unambiguously confirm the structural assignment. Detailed mechanistic analysis based on ab initio density functional theory calculations reveals a stepwise mechanism featuring a rate determining barrier of only ΔE⧧ = 0.6 eV, consistent with the experimentally observed reaction conditions

Re-entrance and entanglement in the one-dimensional Bose-Hubbard model

Re-entrance is a novel feature where the phase boundaries of a system exhibit a succession of transitions between two phases A and B, like A-B-A-B, when just one parameter is varied monotonically. This type of re-entrance is displayed by the 1D Bose Hubbard model between its Mott insulator (MI) and superfluid phase as the hopping amplitude is increased from zero. Here we analyse this counter-intuitive phenomenon directly in the thermodynamic limit by utilizing the infinite time-evolving block decimation algorithm to variationally minimize an infinite matrix product state (MPS) parameterized by a matrix size chi. Exploiting the direct restriction on the half-chain entanglement imposed by fixing chi, we determined that re-entrance in the MI lobes only emerges in this approximate when chi >= 8. This entanglement threshold is found to be coincident with the ability an infinite MPS to be simultaneously particle-number symmetric and capture the kinetic energy carried by particle-hole excitations above the MI. Focussing on the tip of the MI lobe we then applied, for the first time, a general finite-entanglement scaling analysis of the infinite order Kosterlitz-Thouless critical point located there. By analysing chi's up to a very moderate chi = 70 we obtained an estimate of the KT transition as t_KT = 0.30 +/- 0.01, demonstrating the how a finite-entanglement approach can provide not only qualitative insight but also quantitatively accurate predictions.Comment: 12 pages, 8 figure

Growth Kinetics in a Phase Field Model with Continuous Symmetry

We discuss the static and kinetic properties of a Ginzburg-Landau spherically symmetric $O(N)$ model recently introduced (Phys. Rev. Lett. {\bf 75}, 2176, (1995)) in order to generalize the so called Phase field model of Langer. The Hamiltonian contains two $O(N)$ invariant fields $\phi$ and $U$ bilinearly coupled. The order parameter field $\phi$ evolves according to a non conserved dynamics, whereas the diffusive field $U$ follows a conserved dynamics. In the limit $N \to \infty$ we obtain an exact solution, which displays an interesting kinetic behavior characterized by three different growth regimes. In the early regime the system displays normal scaling and the average domain size grows as $t^{1/2}$, in the intermediate regime one observes a finite wavevector instability, which is related to the Mullins-Sekerka instability; finally, in the late stage the structure function has a multiscaling behavior, while the domain size grows as $t^{1/4}$.Comment: 9 pages RevTeX, 9 figures included, files packed with uufiles to appear on Phy. Rev.

Morphology and characterisation of the relict facies on the internal continental shelf in the Gulf of Cadiz, between Ayamonte and Huelva (southern Iberian Peninsula)

The objectives of the present paper are the determination of the morphologic characteristics of the superficial Quaternary relict facies on the internal continental shelf in the Gulf of Cadiz, between Ayamonte and Huelva (southern Spain), their characterisation, and their evolution in the final phases of the last eustatic hemicycle. The study area extends from the mouth of the Guadiana River to the mouth of the Tinto-Odiel River, and from the 6 m isobath to the 56 m isobath. High-resolution seismic profiles (3.5 kHz and Geopulse, 175 J), sonographic profiles (SSS, 100 kHz), and bathymetric profiles (Echotrac sounder) were used in this study. Sediment samples were obtained using Van Veen and Shipek drags. Bathymetric, physiographic, lithologic and morphologic analyses were performed to determine the superficial sediment distribution, relict facies distribution, and thickness of the unconsolidated sediment cover. Analysis of the data obtained indicated that the relict facies beaches and coastal barriers associated with coastal spits located in the ancient outlets of the rivers. Relict facies were grouped into well-differentiated depths, indicating that their position on the continental shelf is influenced by the still-stands and the periods of rapid sea-level changes. The nature of the outcropping relict facies shows that their final configuration can be related to the shelf construction processes, as well as to the most important Holocene transgressive phases.Los objetivos de este trabajo son la determinación de las características morfológicas, la caracterización de las facies relictas cuaternarias superficiales y el estudio de su evolución con relación a las fases finales del último hemiciclo eustático en la plataforma continental interna del golfo de Cádiz, entre Ayamonte y Huelva. El área de estudio abarca desde la desembocadura del río Guadiana hasta la del río Tinto-Odiel y desde los 6 m hasta 56 m de profundidad. Se utilizó gran cantidad de material geofísico, en el que se encuentran perfiles sísmicos de alta resolución (3.5 kHz y Geopulse, 175 J), perfiles sonográficos y perfiles batimétricos, además de muestras de sedimentos obtenidas con dragas Van Veen y Shipek. Con esta información se han realizado análisis batimétricos, fisiográficos, litológicos y morfológicos, además de determinar la distribución de los sedimentos superficiales y de las facies relictas y de cuantificar la potencia de la cobertera sedimentaria. Con todos los datos obtenidos se ha determinado que las facies relictas son interpretadas como playas y cordones litorales asociados a flechas litorales situadas en las antiguas desembocaduras de los ríos. Las formas descritas están agrupadas en zonaciones batimétricas bien diferenciadas, lo que indica que su posición en la plataforma continental está influida por las paradas y etapas de movimiento rápido del nivel del mar. Las características de las facies relictas aflorantes indican que su configuración final puede estar relacionada con los procesos de edificación de la plataforma a partir de las mayores fases transgresivas holocenas.Instituto Español de Oceanografí

The Cadiz Contourite Channel: Sandy contourites, bedforms and dynamic current interaction

The Cadiz Contourite Channel is the largest and most prominent contourite channel in the middle slope of the Gulf of Cadiz, and is known to channelise the southern branch of the Lower Core of Mediterranean Outflow Water (MOW) as it flows westwards from the Gibraltar Gateway. The channel lies in water depth between 650 and 1500 m, is 150 km long, 2–12 km wide, up to 120 m deep, and broadly s-shaped in plan view. It has several associated subparallel marginal channels and shorter spillover channel segments. Its geometry is controlled by the interaction of a strong bottom current with the seafloor morphology, affected by neotectonic deformation and diapiric intrusion. Bottom photographs and dredge hauls reveal a channel floor shaped by high-energy flow, in places with bare rock, boulders and gravel, and elsewhere covered with sandy contourites. The rocky substrate and derived clasts are formed of authigenic iron-rich carbonates, testifying the high degree of fluid escape from adjacent diapiric ridges and mud volcanoes. The sandy substrate shows a wide range of current-induced bedforms including small, straight-crested ripples, large sinuous sand waves and dunes (wavelength 3.5–5 m, height 0.3–0.9 m), weak surface lineation on sands, and aligned gravel stringers and deep erosive scours around large boulders. Bedform orientation indicates flows directed to the south/south-west (main channel) and west (spillover channel), which can be related to MOW bottom currents, and current velocities that vary between about 0.2 and 0.8 m s− 1, even in the same channel location. However, current vane orientation was clearly responding, at least in part, to tidal effects and periodicity in the Gulf of Cadiz at the time the photographs were taken. Maximum current velocities are achieved by a combination of barotropic and internal tides (probably generated at the continental slope) that reinforce the normal MOW flow. In addition, meteorologically-induced internal waves with periods shorter than tidal ones may exert an even greater influence on current intensity, especially when they occur at times of sudden changes of meteorological forcing. This effect further influences MOW variability. In all cases, the funnelling effect of the Cadiz Channel amplifies tidal or meteorologically-induced bottom currents

From hyperextended rift to convergent margin types: mapping the outer limit of the extended Continental Shelf of Spain in the Galicia area according UNCLOS Art. 76

European Geosciences Union General Assembly (2017. Viena)Spain presented on 11 May 2009 a partial submission for delimiting the extended Continental Shelf in respect to the area of Galicia to the Commission on the Limits of the Continental Shelf (CLCS). The Galicia margin represents an example of the transition between two different types of continental margins (CM): a western hyperpextended margin and a northern convergent margin in the Bay of Biscay. The western Galicia Margin (wGM 41º to 43º N) corresponds to a hyper-extended rifted margin as result of the poly-phase development of the Iberian-Newfoundland conjugate margin during the Mesozoic. Otherwise, the north Galicia Margin (nGM) is the western end of the Cenozoic subduction of the Bay of Biscay along the north Iberian Margin (NIM) linked to the Pyrenean-Mediterranean collisional belt.Instituto Geológico y Minero de España, EspañaCentro Oceanográfico de Málaga, Instituto Español de Oceanografía, EspañaInstituto Hidrográfico de la Marina, Españ

MAPPING THE SPAIN´S EXCLUSIVE ECONOMIC ZONE IN THE GALICIAN MARGIN

MAPPING THE SPAIN´S EXCLUSIVE ECONOMIC ZONE IN THE GALICIAN MARGIN Gómez Ballesteros, M.1(*), González-Aller, J-D. 2, Martín Dávila, J. 3, Carbó, A., 4, Somoza, L. 5, Druet, M. 1, Martínez-Espinosa, S. 2, Catalán, M. 3, Muñoz, A. 4, León, R 5 1 Instituto Español de Oceanografía / C/. Corazón de María, 8, 28020 Madrid 2 Instituto Hidrográfico de la Marina / Pl. San Severiano, 3, 11007 Cádiz 3 Real Observatorio de la Armada, C/. Cecilio Pujazón s/n 11100Cádiz 4 Universidad Complutense de Madrid / Av Séneca, 2, 28040 Madrid 5 Instituto Geológico y Minero de España, Calle de Ríos Rosas, 23, 28003 Madrid (*)Corresponding Author: [email protected] In the context of the Hydrographic and Oceanographic Research of the Spain´s Exclusive Economic program (ZEEE), operated jointly by Instituto Hidrográfico de la Marina (IHM) and Real Observatorio de la Armada (ROA) working in close collaboration with the Instituto Español de Oceanografía (IEO), Universidad Complutense de Madrid (UCM) and Instituto Geológico y Minero de España (IGME) have conducted seven oceanographic cruises in Galician waters (EEZ -01 -02 ZEE , ZEE -03, ZEE -06 -07 ZEE , ZEE- ZEE- 08 and 09). The main objective of the Spain´s Exclusive Economic Zone project is mapping the seafloor, carrying out a systematic bathymetric survey of the 200 miles that comprise this area. In addition, as secondary objectives were performed acquiring that complement other geophysical parameters characterizing the seafloor and seabed from the knowledge of other variables such as the Terrestrial Magnetic Field , Terrestrial Gravity field, sound velocity and seabed internal structure. For the acquisition of detailed and accurate information during these cruises, carried on board the BIO Hespérides, high-resolution geophysical techniques were used to compile the data and the bathymetry of the region was mapped using a multibeam system during which 100 per cent coverage was obtained. At the same time high-resolution parametric seismic reflection profiles, as well as gravity and magnetic, were also recorded in the survey areas. These systems provide data on bathymetry, quality seafloor, acoustics backscatter , gravimetry, magnetometry and subsurface structure and require the use of precise positioning techniques, so were used in conjunction with GPSD and inertial navigation systems. As a result of these oceanographic researches and post-processing, analysis and interpretation of the whole acquired data, a synthesis of 6 maps were published with 1:500.000 scale and corresponding to Bathymetric map, Geomorphology map, Geomagnetic Anomaly map, Bouguer and Free Air Anomaly maps and backscatter map. REFERENCIAS J. Martín Davila, M. Catalán, M. Larrán, Sección de Hidrografía del IHM, A. Carbó, A. Muñoz-Martín, JL Granja, P. Llanes, L. Somoza, R. León, F.J. Gonzalez, M. Gómez-Ballesteros, M. Druet, and J. Acosta, 2014: Zona Económica Exclusiva Española (ZEEE): Margen Continental Gallego. Mapas Generales de batimetría, de anomalías Geomagnéticas, Graviméwtricas de Aire Libre y Bpouguer, Geomorfológico y Mosaico de Imágenes de Reflectividad (E. 1:500.000). Ministerio de Defensa. Secretaria General Técnica, NIPO: 083-12-230-3, DL: M-39518-201