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Rare-earth metal-organic frameworks (RE-MOFs) formed in the presence of fluoride donors are a group of complex and applicable MOFs. Determining structural complexity is crucial in applying such MOFs and has been achieved to uncover framework disorders in the important fcu framework topology MOF, Y-ndc- fcu -MOF ( 1 ). 1 is found to contain F - groups disordered over the μ 3 -face-capping sites in its secondary building unit (SBU) and framework distortions upon sorption of different guest molecules. The favored location of the guests is within the octahedral cage of 1 where they interact with the Y 3+ centers. The size, shape, and interactions of the different guests lead to subtle distortions within the SBU and adoption of specific orientations of the naphthalene group of the 1,4-naphthalenedicarboxylate framework linkers. The sorption of DMF (l) /H 2 O (l) lowers the symmetry from cubic Fm 3̅ m (for MeOH (l) , N 2(g) , CO 2(g or l) ) to cubic Pa 3̅ (for DMF (l) /H 2 O (l) ) symmetry with retention of the fcu topology, and conversion between the Pa 3̅ and Fm 3̅ m structures is induced by solvent exchange. Such disorder and sorption locations and transformation are important considerations during the optimization and application of MOFs for sorption-based technologies.

Mono- and bis-salen functionalised [2]rotaxanes have been synthesised from the esterification of [2]rotaxanes containing phenol-terminated threads (salen=N,N'-bis(salicylidene)ethylenediamine). The [2]rotaxanes have general formula [RH][Cr 7 NiF 8 (O 2 C t Bu) 16 ], where [RH] + is a thread with a central secondary ammonium site that templates a [Cr 7 NiF 8 (O 2 C t Bu) 16 ] - ring. The threads are terminated at one or both ends by carboxylic acid functionalised salen groups. The {M(salen)} groups can be free-base [M=(H + ) 2 ] or metallated [M=Cu 2+ , Ni 2+ , (VO) 2+ ]. The [2]rotaxanes have been characterised by single crystal XRD and solid- and solution-state EPR spectroscopy. Where two paramagnetic M ions are involved [M=Cu 2+ and/or (VO) 2+ ] the [2]rotaxanes contain three electron spin S= 1 / 2 ${{ 1/2 }}$ centres, since the {Cr 7 Ni} ring has an S= 1 / 2 ${{ 1/2 }}$ ground state which is well isolated at low temperatures. These three-spin [2]rotaxanes have been characterised in solution by pulsed dipolar EPR spectroscopies (DEER, also known as PELDOR, and RIDME). The M⋅⋅⋅M and M⋅⋅⋅{Cr 7 Ni} interactions measured are consistent with dipolar interactions and also with the distances from single crystal XRD. The authors declare no competing financial interest., (© 2024 The Authors. Chemistry - An Asian Journal published by Wiley-VCH GmbH.)

In the design of dynamic supramolecular systems used in molecular machines, it is important to understand the binding preferences between the macrocycle and stations along the thread. Here, we apply 1 H NMR spectroscopy to investigate the relative stabilities of a series of linear alkylammonium templated pseudorotaxanes with the general formula [H 2 NRR'][Cr 7 CoF 8 (O 2 CCH 2 t Bu) 16 ] by exchanging the cation in solution. Our results show that the pseudorotaxanes are able to exchange threads via a dissociative mechanism. The position of equilibrium is dependent upon the ammonium cation and solvent used. Short chain primary ammonium cations are shown to be far less favourable macrocycle stations than secondary ammonium cations. Collision-induced dissociation mass spectrometry (CID-MS) has been used to look at disassembly of the pseudorotaxanes in a solvent-free environment and stability trends compared to those in acetone-d6. The energy needed to induce 50 % of the precursor ion loss (E 50 ) is used and shows a similar trend to the equilibria measured by NMR. The relative stabilities of these hybrid inorganic-organic pseudo-rotaxanes are different to those of host-guest compounds involving crown ethers and this may be valuable for the design of molecular machines., (© 2024 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

A synthetic strategy is demonstrated to prepare two distinct trimers of antiferromagnetically coupled {Cr 7 Ni} rings, substantially varying the magnetic interactions between the spin centres. The interactions were studied using multi-frequency cw EPR: in a trimer linked via non-covalent H-bonding interactions no measurable interaction between rings was seen, while in a trimer linked via iso-nicotinate groups isotropic and anisotropic exchange interactions of +0.42 and -0.8 GHz, respectively, were observed. The latter are the same as those for a simpler hetero-dimer system, showing how the spin-spin interactions can be built in a predictable and modular manner in these systems., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Here we report the synthesis and structural characterization of four [7]rotaxanes formed by coordinating hybrid inorganic-organic [2]rotaxanes to a central {Ni 12 } core. X-ray single crystal diffraction demonstrate that [7]rotaxanes are formed, with a range of conformations in the crystal. Small angle X-ray scattering supported by molecular dynamic simulations demonstrates that the large molecules are stable in solution and also show that the conformers present in solution are not those found in the crystal. Pulsed EPR spectroscopy show that phase memory times for the {Cr 7 Ni} rings, which have been proposed as qubits, are reduced but not dramatically by the presence of the {Ni 12 } cage., Competing Interests: The authors declare no competing financial interest., (This journal is © the Partner Organisations.)

Proton-exchange membrane fuel cells enable the portable utilization of hydrogen (H 2 ) as an energy resource. Current electrolytic materials have limitation, and there is an urgent need to develop new materials showing especially high proton conductivity. Here, we report the ultra-fast proton conduction in a novel metal-organic framework, MFM-808, which adopts an unprecedented topology and a unique structure consisting of two-dimensional layers of {Zr 6 }-clusters. By replacing the bridging formate with sulfate ligands within {Zr 6 }-layers, the modified MFM-808-SO 4 exhibits an exceptional proton conductivity of 0.21 S·cm -1 at 85 °C and 99% relative humidity. Modeling by molecular dynamics confirms that proton transfer is promoted by an efficient two-dimensional conducting network assembled by sulfate-{Zr 6 }-layers. MFM-808-SO 4 also possesses excellent photocatalytic activity for water splitting to produce H 2 , paving a new pathway to achieve a renewable hydrogen-energy cycle.

Despite being known for decades, the solution-state molecular chemistry of heptapnictogen ([Pn 7 ] 3- ; Pn = P, As) clusters is not well established. Here we study heavy element derivatives of tetrel functionalized heptapnictogen clusters towards heteroallene capture, specifically isocyanates, an isothiocyanate and CO 2 are probed. Clusters (Me 3 Ge) 3 P 7 (1), (Et 3 Ge) 3 P 7 (2), ( n Bu 3 Sn) 3 P 7 (3), and (Me 3 Si) 3 As 7 (4) were all found to capture isocyanates between all three of their tetrel-pnictogen bonds. In the case of phenyl isocyanate insertion, tetrel coordination at the isocyanate nitrogen atoms is preferred, while in the case of p -toluenesulfonyl isocyanate insertion, tetrel coordination at oxygen is preferred. Furthermore, the reaction of (Me 3 Si) 3 P 7 with CO 2 gave NMR spectra consistent with the capture of the greenhouse gas. Heteroallene insertion at these clusters was also studied using density functional theory.

The first fully characterized boron-functionalized heptaphosphide Zintl cluster, [(BBN)P 7 ] 2- ([ 1 ] 2- ), is synthesized by dehydrocoupling [HP 7 ] 2- . Dehydrocoupling is a previously unprecedented reaction pathway to functionalize Zintl clusters. [Na(18-c-6)] 2 [ 1 ] was employed as a transition metal-free catalyst for the hydroboration of aldehydes and ketones. Moreover, the greenhouse gas carbon dioxide (CO 2 ) was efficiently and selectively reduced to methoxyborane. This work represents the first examples of Zintl catalysis where the transformation is transition metal-free and where the cluster is noninnocent.

Carbene-metal-amides (CMAs) are an emerging class of photoemitters based on a linear donor-linker-acceptor arrangement. They exhibit high flexibility about the carbene-metal and metal-amide bonds, leading to a conformational freedom which has a strong influence on their photophysical properties. Herein we report CMA complexes with (1) nearly coplanar, (2) twisted, (3) tilted, and (4) tilt-twisted orientations between donor and acceptor ligands and illustrate the influence of preferred ground-state conformations on both the luminescence quantum yields and excited-state lifetimes. The performance is found to be optimum for structures with partially twisted and/or tilted conformations, resulting in radiative rates exceeding 1 × 10 6 s -1 . Although the metal atoms make only small contributions to HOMOs and LUMOs, they provide sufficient spin-orbit coupling between the low-lying excited states to reduce the excited-state lifetimes down to 500 ns. At the same time, high photoluminescence quantum yields are maintained for a strongly tilted emitter in a host matrix. Proof-of-concept organic light-emitting diodes (OLEDs) based on these new emitter designs were fabricated, with a maximum external quantum efficiency (EQE) of 19.1% with low device roll-off efficiency. Transient electroluminescence studies indicate that molecular design concepts for new CMA emitters can be successfully translated into the OLED device., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Despite being known for decades the chemical reactivity of homoatomic seven-atom phosphorus clusters towards small molecules remains largely unexplored. Here, we report that neutral tris(silyl) functionalised heptaphosphane (P 7 (SiR 3 ) 3 ) cages are capable of heteroallene capture between the P-Si bonds of the cluster. A range of isocyanates and an isothiocyanate were investigated. In the case of isocyanates, silyl bonding at oxygen or nitrogen is regioselectively directed by the functional group on the isocyanate and substituents on the silyl moiety. Above all, we find that captured isothiocyanate molecules can be exchanged for isocyanate molecules, indicative of small molecule catch and release. Small molecule catch and release at these Zintl-derived clusters reveals their potential application as chemical storage materials or as reusable probes., (© 2021 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Emerging clinical data from the current COVID-19 pandemic suggests that ~ 40% of COVID-19 patients develop neurological symptoms attributed to viral encephalitis while in COVID long haulers chronic neuro-inflammation and neuronal damage result in a syndrome described as Neuro-COVID. We hypothesize that SAR-COV2 induces mitochondrial dysfunction and activation of the mitochondrial-dependent intrinsic apoptotic pathway, resulting in microglial and neuronal apoptosis. The goal of our study was to determine the effect of SARS-COV2 on mitochondrial biogenesis and to monitor cell apoptosis in human microglia non-invasively in real time using Raman spectroscopy, providing a unique spatio-temporal information on mitochondrial function in live cells. We treated human microglia with SARS-COV2 spike protein and examined the levels of cytokines and reactive oxygen species (ROS) production, determined the effect of SARS-COV2 on mitochondrial biogenesis and examined the changes in molecular composition of phospholipids. Our results show that SARS- COV2 spike protein increases the levels of pro-inflammatory cytokines and ROS production, increases apoptosis and increases the oxygen consumption rate (OCR) in microglial cells. Increases in OCR are indicative of increased ROS production and oxidative stress suggesting that SARS-COV2 induced cell death. Raman spectroscopy yielded significant differences in phospholipids such as Phosphatidylinositol (PI), phosphatidylserine (PS), phosphatidylethanolamine (PE) and phosphatidylcholine (PC), which account for ~ 80% of mitochondrial membrane lipids between SARS-COV2 treated and untreated microglial cells. These data provide important mechanistic insights into SARS-COV2 induced mitochondrial dysfunction which underlies neuropathology associated with Neuro-COVID., (© 2021. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Manganese(II) xanthate complexes of the form [Mn(S 2 COR) 2 (TMEDA)], where TMEDA = tetramethylethylenediamine and R = methyl ( 1 ), ethyl ( 2 ), n -propyl ( 3 ), n -butyl ( 4 ), n -pentyl ( 5 ), n -hexyl ( 6 ), and n -octyl ( 7 ), have been synthesized and structures elucidated using single-crystal X-ray diffraction. Complexes 1 - 7 were used as molecular precursors to synthesize manganese sulfide (MnS). Olelyamine-capped nanocrystals have been produced via hot injection, while the doctor blading followed by thermolysis yielded thick films. Free-standing polycrystalline powders of MnS are produced by direct thermolysis of precursor powders. All thermolysis techniques produced cubic MnS, as confirmed by powder X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy, and Raman spectroscopy. Magnetic measurements reveal that the α-MnS nanocrystals exhibit ferromagnetic behavior with a large coercive field strength ( e.g., 0.723 kOe for 6.8 nm nanocrystals)., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

With the recent increase in research into ferroelectric, anti-ferroelectric and piezoelectric materials, studying the solid-state properties in situ under applied electric fields is vital in understanding the underlying processes. Where this behaviour is the result of atomic displacements, crystallographic insight has an important role. This work presents a sample environment designed to apply an electric field to single-crystal samples in situ on the small-molecule single-crystal diffraction beamline I19, Diamond Light Source (UK). The configuration and operation of the cell is described as well as its application to studies of a proton-transfer colour-change material., (© Lucy K. Saunders et al. 2021.)

The implementation of a quantum computer requires both to protect information from environmental noise and to implement quantum operations efficiently. Achieving this by a fully fault-tolerant platform, in which quantum gates are implemented within quantum-error corrected units, poses stringent requirements on the coherence and control of such hardware. A more feasible architecture could consist of connected memories, that support error-correction by enhancing coherence, and processing units, that ensure fast manipulations. We present here a supramolecular {Cr 7 Ni}-Cu system which could form the elementary unit of this platform, where the electronic spin 1/2 of {Cr 7 Ni} provides the processor and the naturally isolated nuclear spin 3/2 of the Cu ion is used to encode a logical unit with embedded quantum error-correction. We demonstrate by realistic simulations that microwave pulses allow us to rapidly implement gates on the processor and to swap information between the processor and the quantum memory. By combining the storage into the Cu nuclear spin with quantum error correction, information can be protected for times much longer than the processor coherence., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

MFM-722(Pb)-DMA undergoes a single-crystal-to-single-crystal (SCSC) transformation to give MFM-722(Pb)-H2O via ligand substitution upon exposure to water vapour. In situ single crystal impedance spectroscopy reveals an increase in proton conductivity due to this structural transition, with MFM-722(Pb)-H2O showing a proton conductivity of 6.61 × 10-4 S cm-1 at 50 °C and 98% RH. The low activation energy (Ea = 0.21 eV) indicates that the proton conduction follows a Grotthuss mechanism.

Reduction of copper(ii) chloride using sodium ascorbate in the presence of pure sodium 5-nitro-tetrazolate (NaNT) forms copper(i) 5-nitrotetrazolate - a known initiatory explosive (DBX-1) - and the novel mixed-ligand copper(i) chloride 5-nitrotetrazolate coordination polymer Cu3Cl(N4C-NO2)2, as well as mixtures of both. The reaction is controlled by the presence of seed crystals and transition metal compounds other than CuCl2. Cu3Cl(N4C-NO2)2 is obtained as a wine-red, air stable, water-insoluble, crystalline and highly sensitive explosive material with a greater crystal density, lower thermal stability and a higher sensitivity toward hydrolysis and shock than DBX-1. Efforts to obtain the stable and pure starting material are improved by crystallisation of NaNT as a tetrahydrate. Cu3Cl(N4C-NO2)2 and Na(H2O)4(NT) were characterised by single crystal and powder XRD, IR spectroscopy, magnetic and thermal measaurements, elemental analysis, particle size measurements, mass spectrometry, and by drop weight testing.

Four 3d-4f hetero-polymetallic complexes [Fe 2 Ln 2 ((OCH 2 ) 3 CR) 2 (O 2 C t Bu) 6 (H 2 O) 4 ] (where Ln = La ( 1 and 2 ) and Gd ( 3 and 4 ); and R = Me ( 1 and 3 ) and Et ( 2 and 4 )) are synthesized and analyzed using elemental analysis, Fourier transform infrared spectroscopy, thermogravimetric analysis, and SQUID magnetometry. Crystal structures are obtained for both methyl derivatives and show that the complexes are isostructural and adopt a defective dicubane topology. The four heavy metals are connected with two alkoxide bridges. These four precursors are used as single-source precursors to prepare rare-earth orthoferrite pervoskites of the form LnFeO 3 . Thermal decomposition in a ceramic boat in a tube furnace gives orthorhombic LnFeO 3 powders using optimized temperatures and decomposition times: LaFeO 3 formed at 650 °C over 30 min, whereas GdFeO 3 formed at 750 °C over 18 h. These materials are structurally characterized using powder X-ray diffraction, Raman spectroscopy, scanning electron microscopy, energy-dispersive X-ray map spectroscopy, and SQUID magnetometry. EDX spectroscopy mapping reveals a homogeneous spatial distribution of elements for all four materials consistent with LnFeO 3 . Magnetic measurements on complexes 1 - 4 confirm the presence of weak antiferromagnetic coupling between the central Fe(III) ions of the clusters and negligible ferromagnetic interaction with peripheral Gd(III) ions in 3 and 4 . Zero-field-cooled and field-cooled measurements of magnetization of LaFeO 3 and GdFeO 3 in the solid-state suggest that both materials are ferromagnetic, and both materials show open magnetic hysteresis loops at 5 and 300 K, with M sat higher than previously reported for these nanomaterials. We conclude that this is a new and facile low temperature route to these important magnetic materials that is potentially universal, limited only by what metals can be programmed into the precursor complexes.

The synthesis, structures, and properties of [4]- and [3]-rotaxane complexes are reported where [2]-rotaxanes, formed from heterometallic {Cr 7 Ni} rings, are bound to a fluoride-centered {CrNi 2 } triangle. The compounds have been characterized by single-crystal X-ray diffraction and have the formulas [CrNi 2 (F)(O 2 C t Bu) 6 ]{( B H)[Cr 7 NiF 8 (O 2 C t Bu) 16 ]} 3 ( 3 ) and [CrNi 2 (F)(O 2 C t Bu) 6 (THF)]{( B H)[Cr 7 NiF 8 (O 2 C t Bu) 16 ]} 2 ( 4 ), where B = py-CH 2 CH 2 NHCH 2 C 6 H 4 SCH 3 . The [4]-rotaxane 3 is an isosceles triangle of three [2]-rotaxanes bound to the central triangle while the [3]-rotaxane 4 contains only two [2]-rotaxanes bound to the central triangle. Studies of the behavior of 3 and 4 in solution by small-angle X-ray scattering and atomistic molecular dynamic simulations show that the structure of 3 is similar to that found in the crystal but that 4 has a different conformation to the crystal. Continuous wave and pulsed electron paramagnetic resonance spectroscopy was used to study the structures present and demonstrate that in frozen solutions (at 5 K) 4 forms more extended molecules than 3 and with a wider range of conformations.

Cancer cells survive and adapt to many types of stress including hypoxia, nutrient deprivation, metabolic, and oxidative stress. These stresses are sensed by diverse cellular signaling processes, leading to either degradation of mitochondria or alleviation of mitochondrial stress. This review discusses signaling during sensing and mitigation of stress involving mitochondrial communication with the endoplasmic reticulum, and how retrograde signaling upregulates the mitochondrial stress response to maintain mitochondrial integrity. The importance of the mitochondrial unfolded protein response, an emerging pathway that alleviates cellular stress, will be elaborated with respect to cancer. Detailed understanding of cellular pathways will establish mitochondrial stress response as a key mechanism for cancer cell survival leading to cancer progression and resistance, and provide a potential therapeutic target in cancer., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Objective: Plantar fasciitis is a common cause of heel pain. The aetiology of this condition remains unclear. Patients typically have pain upon palpation of the medial plantar calcaneal region. Extracorporeal shockwave therapy has shown favourable outcomes in various studies. The aim of this study was to compare the effect of focused extracorporeal shockwave therapy with radial pressure wave therapy., Patients and Methods: Seventy-nine non-randomised patients diagnosed with plantar fasciitis were included between January 2017 and June 2018. Patients from the Arnau de Vilanova Hospital in Valencia were treated with focused extracorporeal shockwave therapy, and patients from Llíria Hospital with radial pressure wave therapy. Measured outcome variables were: visual analog scale; ultrasonographic measurement of plantar fascia thickness; self-reported foot-specific pain and disability using the Foot Function Index; self-reported health-related quality of life using the Euroqol-5D; self-reported pain and limitations of activity using the Roles & Maudsley Scale., Results: At inclusion, the 2groups showed no significant differences in demographic or clinical characteristics. Three months after treatment completion, both groups showed improvement in all outcome variables, without statistically significant differences between the 2groups. No adverse effects or complications were observed., Conclusions: Both extracorporeal shockwave therapy and radial pressure wave therapy are effective treatments for plantar fasciitis., (Copyright © 2019 Sociedad Española de Rehabilitación y Medicina Física. Publicado por Elsevier España, S.L.U. All rights reserved.)

Multifocal osteonecrosis is defined as the presence of osteonecrosis in three or more osseous sites. It is an infrequent entity representing less than 3% of cases among osteonecrosis patients. Multifocal osteonecrosis has been associated with systemic diseases, with patients at highest risk being those with lupus erythematosus, transplant recipients and those with haematological disorders or prolonged high-dose glucocorticoid treatment. The area most prone to disturbances is the femoral head. The pathogenesis of this particular disorder has not been fully defined, although several risk factors have been identified. We report the case of a young woman with abnormal hemostatic factors and a history of glucocorticoid and oral contraceptive therapy who developed bilateral hip osteonecrosis, followed by shoulder ON. The present article also provides an extensive literature review of the aetiology and treatment of multifocal ON., (Copyright © 2019 Sociedad Española de Rehabilitación y Medicina Física. Publicado por Elsevier España, S.L.U. All rights reserved.)

Historic coastal structures have played a key role in small- to medium-size ports, being the driving force for the local development of coastal communities. Because coastal managers require reliable risk-based analysis of the whole life cycle of these coastal structures, previous lifetimes should be studied. This is a differentiating factor with respect to the newly built breakwaters. For this reason, in this work, a methodology for assessing how the hydraulic performance of an expired lifetime has evolved over the years is presented. It is performed following a probabilistic approach due to the uncertainty related to both the involved variables (wave climate, geometrical and structural breakwater variables) and the hydraulic response of the structure. The first ones are characterized by reliable probability distribution functions. The second ones are characterized by reliable formulae for the analysis of the hydraulic response. However, their non-conventional designs located in shallow-water locations require site-dependent formulae. To overcome this problem, a novel methodology to apply CFD numerical models is presented. Finally, it is integrated in a high-resolution time-dependent probabilistic methodology which takes into account the stochastic behaviour of all the involved variables, coastal and structural processes with a good uncertainty level. This article is part of the theme issue 'Environmental loading of heritage structures'.

A fundamental bonding model in coordination and organometallic chemistry is the synergic, donor-acceptor interaction between a metal and a neutral π-acceptor ligand, in which the ligand σ donates to the metal, which π back-bonds to the ligand. This interaction typically involves a metal with an electron-rich, mid-, low- or even negative oxidation state and a ligand with a π* orbital. Here, we report that treatment of a uranium-carbene complex with an organoazide produces a uranium(V)-bis(imido)-dinitrogen complex, stabilized by a lithium counterion. This complex, which was isolated in a crystalline form, involves an electron-poor, high-oxidation-state uranium(V) 5f 1 ion that is π back-bonded to the poor π-acceptor ligand dinitrogen. We propose that this is made possible by a combination of cooperative heterobimetallic uranium-lithium effects and the presence of suitable ancillary ligands that render the uranium ion unusually electron rich. This electron-poor back-bonding could have implications for the field of dinitrogen activation.

[2] and [3] hybrid rotaxanes are reported based on {Ti 7 M} rings (M is a trivalent metal such as Fe III or Ga III ). NMR studies show that [2]rotaxanes can act as molecular shuttles, while EPR studies of [3]rotaxanes show weak interactions between the paramagnetic components of the supramolecular assemblies., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A family of heterometallic [Cat][Ti x MO (x+1 )(O 2 C t Bu) 2x+2 ] rings is reported where Cat=a secondary or tertiary alkyl ammonium ion, x=7, 8 or 9, and M=Fe III , Ga III , Cr III , In III and Al III . The structures are regular polygons with eight, nine or ten vertices with each edge bridged by an oxide and two pivalates. The size of the ring formed is controlled by the alkylammonium cation present. In each case a homometallic by-product is found [Cat][Ti x O (x+1 )(O 2 C t Bu) 2x-1 ]., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Coastal communities throughout the world are exposed to numerous and increasing threats, such as coastal flooding and erosion, saltwater intrusion and wetland degradation. Here, we present the first global-scale analysis of the main drivers of coastal flooding due to large-scale oceanographic factors. Given the large dimensionality of the problem (e.g. spatiotemporal variability in flood magnitude and the relative influence of waves, tides and surge levels), we have performed a computer-based classification to identify geographical areas with homogeneous climates. Results show that 75% of coastal regions around the globe have the potential for very large flooding events with low probabilities (unbounded tails), 82% are tide-dominated, and almost 49% are highly susceptible to increases in flooding frequency due to sea-level rise.

The first regular homometallic ring containing an odd number of metal centers is reported. The ring was synthesized by means of amine-templated self-assembly. Extensive physical characterization studies, including magnetic measurements, powder inelastic neutron scattering (INS), and DFT calculations, show that the molecule has a near perfect match to the expected behavior for a frustrated system with the lowest energy pair of S=1/2 spin states separated by only 0.1 meV (0.8 cm(-1) )., (© 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

The complete mol-ecule of the title compound, C26H30N4O4, is generated by crystallographic inversion symmetry. The dihedral angle between the planes of the benzene and pyrrole rings is 45.20 (11)°; the N atom bonded to the the benzene ring and the pyrrole N atom are in a syn conformation. The side chain adopts an extended conformation [N-C-C-C = 169.07 (17)° and C-O-C-C = -176.54 (17)°]. No directional inter-actions could be identified in the crystal packing.

The whole mol-ecule of the title compound, C24H32N4O4, is generated by inversion symmetry. The cyclo-hexane ring adopts a chair conformation and the conformation about the C=N bonds is E. The pyrrole rings have an anti confirmation with respect to the cyclo-hexane moiety and the ethyl acetate groups have extended conformations. In the crystal, mol-ecules are linked by pairs of C-H⋯O hydrogen bonds forming chains, enclosing R 2 (2)(10) ring motifs with inversion symmetry, propagating parallel to the (101) plane.

A [2]rotaxane was produced through the assembly of a picolinaldehyde, an amine, and a bipyridine macrocycle around a Cu(I) template by imine bond formation in close-to-quantitative yield. An analogous [3]rotaxane is obtained in excellent yield by replacing the amine with a diamine, thus showing the suitability of the system for the construction of higher order interlocked structures. The rotaxanes are formed within a few minutes simply through mixing the components in solution at room temperature and they can be isolated through removal of the solvent or precipitation., (© 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report the synthesis and characterization of the uranium(III) triamide complex [U(III) (N**)3 ] [1, N**=N(SiMe2 tBu)2 (-) ]. Surprisingly, complex 1 exhibits a trigonal planar geometry in the solid state, which is unprecedented for three-coordinate actinide complexes that have exclusively adopted trigonal pyramidal geometries to date. The characterization data for [U(III) (N**)3 ] were compared with the prototypical trigonal pyramidal uranium(III) triamide complex [U(III) (N")3 ] (N"=N(SiMe3 )2 (-) ), and taken together with theoretical calculations it was concluded that pyramidalization results in net stabilization for [U(III) (N")3 ], but this can be overcome with very sterically demanding ligands, such as N**. The planarity of 1 leads to favorable magnetic dynamics, which may be considered in the future design of U(III) single-molecule magnets., (© 2014 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.)

Aberrant dopamine release in the prefrontal cortex (PFC) is believed to underlie schizophrenia, but the mechanistic pathway through which a widely used antipsychotic, clozapine (Clz), evokes neurotransmitter-releasing electrical stimulation is unclear. We analyzed Clz-evoked regulation of neuronal activity in the PFC by stimulating axons in layers IV and V and recording the electrical effect in the post-synaptic pyramidal cells of layers II and III. We observed a Clz-evoked increase in population spike (PS), which was mediated by serotonin 1A receptor (5-HT(1A)-R), phospholipase Cβ, and Ca(2+)/calmodulin-dependent protein kinase II (CaMKII). Immunoblotting demonstrated that the Clz-activation of CaMKII was 5-HT(1A)-R-mediated. Intriguingly, the NMDA receptor (NMDA-R) antagonist (±)2-amino-5-phosphonovaleric acid (APV) eliminated the Clz-mediated increase in PS, suggesting that the 5-HT(1A)-R, NMDA-R and CaMKII form a synergistic triad, which boosts excitatory post-synaptic potential (EPSP), thereby enhancing PS. In corroboration, Clz as well as NMDA augmented field EPSP (fEPSP), and WAY100635 (a 5-HT(1A)-R antagonist), APV, and a CaMKII inhibitor eliminated this increase. As previously shown, CaMKII binds to the NMDA-R 2B (NR2B) subunit to become constitutively active, thereby inducing α-amino-3-hydroxyl-5-methyl-4-isoxazole-propionate (AMPA) receptor recruitment to the post-synaptic membrane and an increase in fEPSP. Co-immunoprecipitation demonstrated that Clz potentiates interactions among CaMKII, NR2B, and 5-HT(1A)-R, possibly in the membrane rafts of the post-synaptic density (PSD), because pretreatment with methyl-β-cyclodextrin (MCD), an agent that disrupts rafts, inhibited both co-immunoprecipitation as well as fEPSP. In summary, Clz functions in the PFC by orchestrating a synergism among 5-HT(1A)-R, CaMKII, and NMDA-R, which augments excitability in the PFC neurons of layers II/III., (© 2011 The Authors. Journal of Neurochemistry © 2011 International Society for Neurochemistry.)

Aim: This study analyzes the productivity and visibility of Spanish publications in the area of clinical neurology in the period 2000-2009 and compared with those for Italy, France and Germany., Materials and Methods: We used the database Web of Science. The analysis (annual and in five-year) was restricted to the citable documents (original articles, reviews and proceedings papers). Bibliometric indicators used were the number of publications, citations received by publications and Hirsch's h-index. We also assessed the slope of the annual growth rate (b), the number of publications by language and the international collaboration., Results: In the period 2000-2009 there were 46,114 publications in neurology clinic of which 6,998 were Spanish publications (h = 75), 11,629 in Italy (h = 101), French 9,745 (h = 102) and 20,143 in Germany (h = 124). The rate of increase in the total number of publications in Spain (b = 15) was lower than that observed in Italy (b = 65), Germany (b = 61) or France (b = 34). In the case of publications in English, the growth rate was higher for Spain (b = 37) than for France (b = 36) but lower than for Germany (b = 54) and Italy (b = 65)., Conclusions: Although the total number of publications and the observed increase are lower in Spain compared to Italy, France or Germany, the Spanish publications in Clinical Neurology shows good trend indicators with regard to publications in English and international collaboration. This improvement was associated with greater visibility as showed by the five-year analysis of citations received by Spanish publications.

In this work, the benefits of high-frequency (HF) radar currents for oil spill modeling and trajectory analysis of floating objects are analyzed. The HF radar performance is evaluated by means of comparison between a drifter buoy trajectory and the one simulated using a Lagrangian trajectory model. A methodology to optimize the transport model performance and to calculate the search area of the predicted positions is proposed. This method is applied to data collected during the Galicia HF Radar Experience. This experiment was carried out to explore the capabilities of this technology for operational monitoring along the Spanish coast. Two long-range HF radar stations were installed and operated between November 2005 and February 2006 on the Galician coast. In addition, a drifter buoy was released inside the coverage area of the radar. The HF radar currents, as well as numerical wind data were used to simulate the buoy trajectory using the TESEO oil spill transport model. In order to evaluate the contribution of HF radar currents to trajectory analysis, two simulation alternatives were carried out. In the first one, wind data were used to simulate the motion of the buoy. In the second alternative, surface currents from the HF radar were also taken into account. For each alternative, the model was calibrated by means of the global optimization algorithm SCEM-UA (Shuffled Complex Evolution Metropolis) in order to obtain the probability density function of the model parameters. The buoy trajectory was computed for 24h intervals using a Monte Carlo approach based on the results provided in the calibration process. A bivariate kernel estimator was applied to determine the 95% confidence areas. The analysis performed showed that simulated trajectories integrating HF radar currents are more accurate than those obtained considering only wind numerical data. After a 24h period, the error in the final simulated position improves using HF radar currents. Averaging the information from all the simulated daily periods, the mean search and rescue area calculated using HF radar currents, is reduced by approximately a 62% in comparison with the search area calculated without these data. These results show the positive contribution of HF radar currents for trajectory analysis, and demonstrate that these data combined with atmospheric forecast models, are of value for trajectory analysis of oil spills or floating objects.

The formation of cysto-enteric fistula is a rare complication of pseudo-cysts and pancreatic abscess. The etiology, the types, and their treatment are analysed. The authors present a new case of cysto-colonic fistula due to pancreatic abscess after acute pancreatitis, which is the 29th case reported in the literature.