Delamination of 2D coordination polymers: The role of solvent and ultrasound.

Two novel cadmium-based 2D coordination polymers have been synthesized and characterized. Experimental results evidence that the best delamination processes occurs when weak interactions dominate the cohesion between layers and solvent molecules are occluded within the crystalline network. In this case, the delamination of the crystals occurs spontaneously in water. On top of that, and thanks to the high stability of the resulting (flake) colloidal dispersions, we have completed a detailed study of the sonication assisted delamination impact by: I) comparison of two different sonication approaches (bath vs. tip sonication) and II) optimization of final flake morphology and yield by controlling solvent and sonication time. Our results definitely pave the way for the fabrication and implementation of 2D coordination polymers using ultrasound.

The Chemistry behind Catechol-Based Adhesion.

The adhesion of some marine organisms to almost any kind of surface in wet conditions has aroused increasing interest in recent decades. Numerous fundamental studies have been performed to understand the scientific basis of this behaviour, with catechols having been found to play a key role. Several novel bio-inspired adhesives and coatings with value-added performances have been developed by taking advantage of the knowledge gained from these studies. To date there has been no detailed overview focusing exclusively on the complex mode of action of these materials. The aim of this Review is to present recent investigations that elucidate the origin of the strong and versatile adsorption capacities of the catechol moiety and the effects of extrinsic factors that play important roles in the overall adhesion process, such as pH value, solvent, and the presence of metal ions. The aim is to detail the chemistry behind the astonishing properties of natural and synthetic catechol-based adhesive materials.

Dual T1/ T2 Nanoscale Coordination Polymers as Novel Contrast Agents for MRI: A Preclinical Study for Brain Tumor.

In the last years, extensive attention has been paid on designing and developing functional imaging contrast agents for providing accurate noninvasive evaluation of pathology in vivo. However, the issue of false-positives or ambiguous imaging and the lack of a robust strategy for simultaneous dual-mode imaging remain to be fully addressed. One effective strategy for improving it is to rationally design magnetic resonance imaging (MRI) contrast agents (CAs) with intrinsic T1/ T2 dual-mode imaging features. In this work, the development and characterization of one-pot synthesized nanostructured coordination polymers (NCPs) which exhibit dual mode T1/ T2 MRI contrast behavior is described. The resulting material comprises the combination of different paramagnetic ions (Fe3+, Gd3+, Mn2+) with selected organic ligands able to induce the polymerization process and nanostructure stabilization. Among them, the Fe-based NCPs showed the best features in terms of colloidal stability, low toxicity, and dual T1/ T2 MRI contrast performance overcoming the main drawbacks of reported CAs. The dual-mode CA capability was evaluated by different means: in vitro phantoms, ex vivo and in vivo MRI, using a preclinical model of murine glioblastoma. Interestingly, the in vivo MRI of Fe-NCPs show T1 and T2 high contrast potential, allowing simultaneous recording of positive and negative contrast images in a very short period of time while being safer for the mouse. Moreover, the biodistribution assays reveals the persistence of the nanoparticles in the tumor and subsequent gradual clearance denoting their biodegradability. After a comparative study with commercial CAs, the results suggest these nanoplatforms as promising candidates for the development of dual-mode MRI CAs with clear advantages.

Solvent-Tuned Supramolecular Assembly of Fluorescent Catechol/Pyrene Amphiphilic Molecules.

The synthesis and structuration of a novel low-molecular-weight amphiphilic catechol compound is reported. The combination of a hydrophilic tail containing a catechol unit and a pyrene-based hydrophobic head favors solvent-tuned supramolecular assembly. Formation of hollow nanocapsules/vesicles occurs in concentrated solutions of polar protic and nonprotic organic solvents, whereas a fibril-like aggregation process is favored in water, even at low concentrations. The emission properties of the pyrene moiety allow monitoring of the self-assembly process, which could be confirmed by optical and electronic microscopy. In organic solvents and at low concentrations, this compound remains in its nonassembled monomeric form. As the concentration increases, the aggregation containing preassociated pyrene moieties becomes more evident up to a critical micellar concentration, at which vesicle-like structures are formed. In contrast, nanosized twist beltlike fibers are observed in water, even at low concentrations, whereas microplate structures appear at high concentrations. The interactions between molecules in different solvents were studied by using molecular dynamics simulations, which have confirmed different solvent-driven supramolecular interactions.

Reactions in ultra-small droplets by tip-assisted chemistry.

The confinement of chemical reactions within small droplets has received much attention in the last few years. This approach has been proved successful for the in-depth study of naturally occurring chemical processes as well as for the synthesis of different sets of nanomaterials with control over their size, shape and properties. Different approaches such as the use of self-contained structures or microfluidic generated droplets have been followed over the years with success. However, novel approaches have emerged during the last years based on the deposition of femtolitre-sized droplets on surfaces using tip-assisted lithographic methods. In this feature article, we review the advances made towards the use of these ultra-small droplets patterned on surfaces as confined nano-reactors.

Caso clínico: tortícolis muscular congénita secundaria a parálisis del iv par craneal unilateral / Case report: congenital muscular torticollis due to unilateral fourth nerve palsy

La tortícolis muscular es una deformidad que puede ser congénita o adquirida, caracterizada por una inclinación lateral de la cabeza al hombro, con torsión del cuello y desviación de la cara. La etiología es incierta, aunque se han desarrollado numerosas teorías. Si el diagnóstico es precoz, la tortícolis muscular congénita (TMC) se puede tratar conservadoramente, requiriendo cirugía en raras ocasiones. Presentamos el caso clínico de un paciente diagnosticado de TMC secundaria a parálisis del iv par craneal izquierdo, que fue diagnosticado después de 4 años tras varias exploraciones oftalmológicas sin hallazgos. Para llegar a un diagnóstico precoz es necesario hacer un buen diagnóstico diferencial (AU)

Muscular torticollis is a deformity that can be congenital or acquired and is characterised by lateral inclination of the head to the shoulder, with torsion of the neck and deviation of the face. The aetiology is uncertain, although many theories have been developed. If an early diagnosis is made, congenital muscular torticollis (CMT) can be treated conservatively and rarely requires surgery. We report the case of a 4-year-old boy diagnosed with CMT due to left fourth nerve palsy after several normal visual examinations. An appropriate differential diagnosis is essential to achieve an early diagnosis (AU)

Coordination polymer particles with ligand-centred pH-responses and spin transition.

A bis-catechol ligand connected through an imine bond is used to fabricate switchable coordination polymer particles with pH-tuned spin transition responses.

Synthesis of polydopamine at the femtoliter scale and confined fabrication of Ag nanoparticles on surfaces.

Nanoscale polydopamine motifs are fabricated on surfaces by deposition of precursor femtolitre droplets using an AFM tip and employed as confined reactors to fabricate Ag nanoparticle patterns by in situ reduction of a Ag(+) salt.

Advances on structuring, integration and magnetic characterization of molecular nanomagnets on surfaces and devices.

This critical review represents a concise revision of the different experimental approaches so far followed for the structuration of molecular nanomagnets on surfaces, since the first reports on the field more than ten years ago. Afterwards, a presentation of the different experimental approaches followed for their integration in sensors is described. Such work involves mainly two families of sensors and devices, microSQUIDs sensors and three-terminal devices for single-molecule detection. Finally the last section is devoted to a detailed revision of the different experimental techniques that can be used for the magnetic characterization of these systems on surfaces, ranging from magnetic circular dichroism to magnetic force microscopy. The use of these techniques to characterize other nanostructured magnetic materials, such as nanoparticles, is also revised. The aim is to give a broad overview of the last advances achieved with these techniques and their potential and evolution over the next years.

Resultados funcionales en fracturas de extremidad distal del radio. Tratamiento quirúrgico con placa DVR o tratamiento ortopédico / Functional results in fractures of distal radius. Surgical treatment Vs DVR plate orthopedic treatment

Objetivo: Comparar el resultado funcional del tratamiento conservador mediante reducción cerrada y yeso con la reducción abierta y colocación del sistema placa volar anatómica DVR, en fracturas de EDR después de rehabilitación. Material y método: Estudio retrospectivo de 70 pacientes con 54 años de edad media que sufrieron fractura de EDR. Treinta y cinco fueron tratados conservadoramente y otros 35 con placa DVR. Todos realizaron tratamiento rehabilitador y se valoraron los resultados funcionales a partir del año de la intervención, utilizando la escala de Mayo Wrist Score (MWS). El recorrido articular se midió mediante goniómetro manual y la fuerza con la Escala Cifrada Internacional Resultados: El tiempo desde la intervención hasta que se inició la rehabilitación fue de 57 días de media, con un promedio de 29 sesiones. El resultado funcional mostró un valor medio con la MWS de 88,43/100, al año de la fractura, considerado bueno, sin demostrar diferencias estadísticamente significativas entre los 2 grupos. La reinserción laboral de los sujetos que trabajaban en su antiguo trabajo fue de 88,9%. Conclusiones: El tratamiento de las fracturas de EDR seguido de tratamiento rehabilitador permite una buena recuperación funcional con independencia del tratamiento (AU)

Objetive: Compare the functional outcome of conservative management by closed reduction and cast with open reduction and placement of anatomical volar plate system DVR, in EDR fractures after rehabilitation. Material and Methods: We plan a retrospective study of 70 patients with a mean age of 54 years who suffered a EDR fracture, 35 patient treated conservatively and 35 treated by plate DVR. All carried out rehabilitation treatment and functional outcomes were assessed from the year of the intervention, using the scale de Mayo Wrist Score (MWS). The range of movement was measured by manual goniometer and strength with the scale by international standards. Results: The time from intervention until the beginning of the rehabilitation was 57 days on average, by an average of 28.97 sessions. The functional outcome showed a mean of 88.43/100 with MWS, a year after the fracture, considered good, without showing statistically significant differences between the two groups. The reemployment of individuals who worked in his old job was 88.9%. Conclusions: The treatment of fractures of EDR followed by rehabilitation treatment allows a good functional recovery independent of the treatment (AU)

Assisted-assembly of coordination materials into advanced nanoarchitectures by Dip Pen nanolithography.

Femptolitre droplets deposited on surfaces assisted by an AFM tip are used as reactor vessels to fabricate arrays of nanoarchitectures ranging from single-crystals of metal-organic frameworks to hollow capsules of magnetic polyoxometalates.

Acetylcholinesterase as an amyloid enhancing factor in PrP82-146 aggregation process.

Acetylcholinesterase (AChE) triggers beta amyloid plaques formation and is associated with amyloid plaques in the brain. Recent studies have demonstrated that AChE promotes the aggregation of PrP106-126, a peptide deduced from the prion protein sequence. In the present study we show that AChE triggers also the fibrillization of the main component of the amyloid plaques -the peptide spanning residues 82-146 (PrP82-146)- found in patients with Gerstmann-Sträussler-Scheinker disease (GSS). The kinetics of PrP82-146 aggregate formation was directly correlated with AChE concentration and mature fibrils showed the tinctorial and optical properties of amyloid. Atomic force microscopy analysis showed that oligomer and amyloid fibril formation were significantly accelerated by AChE. This effect was mediated by the peripheral site of the enzyme since propidium iodide inhibited the fibrillization process. Present results strongly support the role of AChE in triggering amyloidogenesis and the potential therapeutic relevance of peripheral site blocker compounds.

Comparación de dos programas de rehabilitación tras artroplastia total de rodilla / Comparison of two rehabilitation programs following total knee arthroplasty

Objetivo: Comparar los resultados funcionales de dos programas de rehabilitación distintos tras Artroplastia Total de Rodilla (ATR). Material y métodos: Estudio prospectivo de 122 pacientes intervenidos de ATR, valorándolos en el preoperatorio, al 8º día y al 6º mes de la intervención. Al alta hospitalaria, dividimos a los pacientes en 2 grupos según el recorrido articular y la disponibilidad de acudir al tratamiento. El grupo A (40 pacientes) siguieron un programa de rehabilitación domiciliario y el grupo B (82 pacientes) ambulatorio. Se estudió: el dolor mediante la escala visual analógica (EVA), la funcionalidad usando el Hospital Special Surgery (HSS), la independencia para las actividades de la vida diaria mediante el Índice de Barthel, la capacidad de marcha con la Fuctional Ambulatory Clasification (FAC) y la calidad de vida con el cuestionario de salud SF-36. Comparamos los resultados usando el paquete estadístico SPSS 15.0. Resultados: La valoración global mostró un mejoría de: 7,2 a 2,4 en la EVA, 63 a 80,8 en el HSS, 27,9 a 37,2 en el SF36 físico y 43,4 a 46,9 entre la valoración inicial y al sexto mes en todos los pacientes, siendo estas mejorías estadísticamente significativas (p < 0,05). No hay una diferencia significativa en el Índice de Barthel y el FAC. En la comparación entre ambos grupos, no encontramos diferencias significativas en ninguna variable. Conclusiones: La ATR mejora el dolor, la funcionalidad y la calidad de vida en pacientes con gonartrosis con independencia de los dos programas de rehabilitación estudiados tras el alta hospitalaria (AU)

Objective: To compare the functional results obtained with two different rehabilitation programs following total knee arthroplasty (TKA). Material and methods: A retrospective study was made of 122 patients subjected to TKA, with evaluation before surgery, and on day 8 and 6 months after the operation. At discharge, the patients were divided into two groups according to the observed joint trajectory and patient availability for treatment. Group A (40 patients) followed a home rehabilitation program, while group B (82 patients) followed an outpatient rehabilitation program. The following was studied: pain as determined by the visual analog scale (VAS); functionality based on the Hospital Special Surgery (HSS) score; independency for activities of daily living based on the Barthel index; walking capacity according to the Functional Ambulatory Classification (FAC); and quality of life based on the SF 36 questionnaire. The results were compared using the SPSS version 15.0 statistical package. Results: The overall assessment showed improvement from 7.2 to 2.4 on the VAS, 63 to 80.8 on the HSS, 27.9 to 37.2 on the physical SF-36, and 43.4 to 46.9 between initial assessment and evaluation after 6 months in all the patients - these improvements being statistically significant (p<0.05). There were no significant differences in the Barthel index and FAC. No significant differences were observed for any variable on comparing the two patient groups. Conclusions: TKA improves pain, functionality and quality of life in patients with gonarthrosis, regardless of whether one or the other rehabilitation program is adopted after hospital discharge (AU)

Long-range ferromagnetism of Mn12 acetate single-molecule magnets under a transverse magnetic field.

We use neutron diffraction to probe the magnetization components of a crystal of Mn12 single-molecule magnets. Each of these molecules behaves, at low temperatures, as a nanomagnet with spin S = 10 and strong anisotropy along the crystallographic c axis. The application of a magnetic field H(perpendicular) perpendicular to c induces quantum tunneling between opposite spin orientations, enabling the spins to attain thermal equilibrium. For T approximately < 0.9(1) K, this equilibrium state shows spontaneous magnetization, indicating the onset of ferromagnetism. These long-range magnetic correlations nearly disappear for mu0H(perpendicular) approximately > 5.5 T, possibly suggesting the existence of a quantum critical point.

Synthesis, structural and magnetic properties of a series of copper(II) complexes containing a monocarboxylated perchlorotriphenylmethyl radical as a coordinating open-shell ligand.

A series of complexes of copper(II)-containing a perchlorotriphenylmethyl radical functionalized with a carboxylic group as a new ligand is reported. The compounds [Cu(PTMMC)(2)(L)(3)](PTMMC = (tetradecachloro-4-carboxytriphenyl)methyl radical; L =(1) H(2)O, (2) pyrimidine and ethanol or (3) pyridine), [Cu(2)(PTMMC)(2)(MeCOO)(2)(H(2)O)(2)](4) and [Cu(HPTMMC)(2)(L)(3)](HPTMMC =alpha-H-(tetradecachlorotriphenyl)methane-4-carboxylic acid; L = pyridine)(5) were structurally characterized. In complexes 1, 2, 3, and 5, the copper(II) ion is coordinated to two PTMMC (or HPTMMC) units in a slightly distorted square planar surrounding, while 4 shows a paddle-wheel copper(II) dimer structure, where each Cu metal ion has four O atoms of different carboxylate groups, two of them belonging to two PTMMC radicals. The copper(II)-radical exchange couplings are antiferromagnetic for complexes 1, 2 and 3. A linear three-spin model was applied to complexes 1, 2 and 3 to give J/k(B)=-24.9, -15.0 and -20.7 K, respectively. Magnetic properties of 4 show that it is one of the scarce examples of a spin-frustrated system composed of organic radicals and metal ions. In this case, experimental data were fitted to a magnetic model based on a symmetrical butterfly arrangement to give a copper(II)-copper(II) exchange coupling of J/k(B)=-350.0 K and a copper(II)-radical exchange coupling of J/k(B)=-21.3 K, similar to that observed for the copper(II)-radical interactions in complexes, and.

Drenaje linfático manual en el linfedema facial / Manual lymph drainage in facial lymphedema

Presentamos la evolución de una paciente de 19 años de edad con un adenoma pleomorfo de parótida que tras varios tratamientos, incluyendo vaciamiento ganglionar cervical y radioterapia, desarrolló linfedema facial. Debido a la repercusión de tipo emocional que originó en la paciente, se planificó tratamiento físico rehabilitador con drenaje linfático manual con el que mejoró tanto subjetiva como objetivamente (AU)

Influence of topology on the long-range electron-transfer phenomenon.

Intramolecular electron-transfer phenomena in the radical anions derived from the partial reduction of diradicals (E,E)-p-divinylbenzene-beta,beta'-ylene bis(4-tetradecachlorotriphenylmethyl) diradical (1) and (E,E)-m-divinylbenzene-beta,beta'-ylene bis(4-tetradecachlorotriphenylmethyl) diradical (2) have been studied by optical and ESR spectroscopy. The synthetic methodology used allows for complete control of the geometry of diradicals 1 and 2, which have para and meta topologies, respectively, as well as of their E/Z isomerism. This fact is used to show the influence of the different topologies on the ease of electron transfer, which is larger for the para than for the meta isomer, in which a small or negligible electronic coupling is observed. A related monoradical compound (E)-bis(pentachlorophenyl)[4-(4-bromophenyl-beta-styryl)-2,3,5,6-tetrachlorophenyl]-methyl radical (3), which has only one such redox site, has also been obtained and studied for comparison purposes.