Condicionantes de la adherencia y anclaje en el refuerzo de muros de fábrica con elementos de fibras

Es cada vez más frecuente la rehabilitación de patrimonio construido, tanto de obras deterioradas como para la adecuación de obras existentes a nuevos usos o solicitaciones. Se ha considerado el estudio del refuerzo de obras de fábrica ya que constituyen un importante número dentro del patrimonio tanto de edificación como de obra civil (sistemas de muros de carga o en estructuras principales porticadas de acero u hormigón empleándose las fábricas como cerramiento o distribución con elementos autoportantes). A la hora de reparar o reforzar una estructura es importante realizar un análisis de las deficiencias, caracterización mecánica del elemento y solicitaciones presentes o posibles; en el apartado 1.3 del presente trabajo se refieren acciones de rehabilitación cuando lo que se precisa no es refuerzo estructural, así como las técnicas tradicionales más habituales para refuerzo de fábricas que suelen clasificarse según se trate de refuerzos exteriores o interiores. En los últimos años se ha adoptado el sistema de refuerzo de FRP, tecnología con origen en los refuerzos de hormigón tanto de elementos a flexión como de soportes. Estos refuerzos pueden ser de láminas adheridas a la fábrica soporte (SM), o de barras incluidas en rozas lineales (NSM). La elección de un sistema u otro depende de la necesidad de refuerzo y tipo de solicitación predominante, del acceso para colocación y de la exigencia de impacto visual. Una de las mayores limitaciones de los sistemas de refuerzo por FRP es que no suele movilizarse la resistencia del material de refuerzo, produciéndose previamente fallo en la interfase con el soporte con el consecuente despegue o deslaminación; dichos fallos pueden tener un origen local y propagarse a partir de una discontinuidad, por lo que es preciso un tratamiento cuidadoso de la superficie soporte, o bien como consecuencia de una insuficiente longitud de anclaje para la transferencia de los esfuerzos en la interfase. Se considera imprescindible una caracterización mecánica del elemento a reforzar. Es por ello que el trabajo presenta en el capítulo 2 métodos de cálculo de la fábrica soporte de distintas normativas y también una formulación alternativa que tiene en cuenta la fábrica histórica ya que su caracterización suele ser más complicada por la heterogeneidad y falta de clasificación de sus materiales, especialmente de los morteros. Una vez conocidos los parámetros resistentes de la fábrica soporte es posible diseñar el refuerzo; hasta la fecha existe escasa normativa de refuerzos de FRP para muros de fábrica, consistente en un protocolo propuesto por la ACI 440 7R-10 que carece de mejoras por tipo de anclaje y aporta valores muy conservadores de la eficacia del refuerzo. Como se ha indicado, la problemática principal de los refuerzos de FRP en muros es el modo de fallo que impide un aprovechamiento óptimo de las propiedades del material. Recientemente se están realizando estudios con distintos métodos de anclaje para estos refuerzos, con lo que se incremente la capacidad última y se mantenga el soporte ligado al refuerzo tras la rotura. Junto con sistemas de anclajes por prolongación del refuerzo (tanto para láminas como para barras) se han ensayado anclajes con llaves de cortante, barras embebidas, o anclajes mecánicos de acero o incluso de FRP. Este texto resume, en el capítulo 4, algunas de las campañas experimentales llevadas a cabo entre los años 2000 y 2013 con distintos anclajes. Se observan los parámetros fundamentales para medir la eficacia del anclajes como son: el modo de fallo, el incremento de resistencia, y los desplazamientos que permite observar la ductilidad del refuerzo; estos datos se analizan en función de la variación de: tipo de refuerzo incluyéndose el tipo de fibra y sistema de colocación, y tipo de anclaje. Existen también parámetros de diseño de los propios anclajes. En el caso de barras embebidas se resumen en diámetro y material de la barra, acabado superficial, dimensiones y forma de la roza, tipo de adhesivo. En el caso de anclajes de FRP tipo pasador la caracterización incluye: tipo de fibra, sistema de fabricación del anclajes y diámetro del mismo, radio de expansión del abanico, espaciamiento longitudinal de anclajes, número de filas de anclajes, número de láminas del refuerzo, longitud adherida tras el anclaje; es compleja la sistematización de resultados de los autores de las campañas expuestas ya que algunos de estos parámetros varían impidiendo la comparación. El capítulo 5 presenta los ensayos empleados para estas campañas de anclajes, distinguiéndose entre ensayos de modo I, tipo tracción directa o arrancamiento, que servirían para sistemas NSM o para cuantificar la resistencia individual de anclajes tipo pasador; ensayos de modo II, tipo corte simple, que se asemeja más a las condiciones de trabajo de los refuerzos. El presente texto se realiza con objeto de abrir una posible investigación sobre los anclajes tipo pasador, considerándose que junto con los sistemas de barra embebida son los que permiten una mayor versatilidad de diseño para los refuerzos de FRP y siendo su eficacia aún difícil de aislar por el número de parámetros de diseño. Rehabilitation of built heritage is becoming increasingly frequent, including repair of damaged works and conditioning for a new use or higher loads. In this work it has been considered the study of masonry wall reinforcement, as most buildings and civil works have load bearing walls or at least infilled masonry walls in concrete and steel structures. Before repairing or reinforcing an structure, it is important to analyse its deficiencies, its mechanical properties and both existing and potential loads; chapter 1, section 4 includes the most common rehabilitation methods when structural reinforcement is not needed, as well as traditional reinforcement techniques (internal and external reinforcement) In the last years the FRP reinforcement system has been adopted for masonry walls. FRP materials for reinforcement were initially used for concrete pillars and beams. FRP reinforcement includes two main techniques: surface mounted laminates (SM) and near surface mounted bars (NSM); one of them may be more accurate according to the need for reinforcement and main load, accessibility for installation and aesthetic requirements. One of the main constraints of FRP systems is not reaching maximum load for material due to premature debonding failure, which can be caused by surface irregularities so surface preparation is necessary. But debonding (or delamination for SM techniques) can also be a consequence of insufficient anchorage length or stress concentration. In order to provide an accurate mechanical characterisation of walls, chapter 2 summarises the calculation methods included in guidelines as well as alternative formulations for old masonry walls as historic wall properties are more complicated to obtain due to heterogeneity and data gaps (specially for mortars). The next step is designing reinforcement system; to date there are scarce regulations for walls reinforcement with FRP: ACI 440 7R-10 includes a protocol without considering the potential benefits provided by anchorage devices and with conservative values for reinforcement efficiency. As noted above, the main problem of FRP masonry walls reinforcement is failure mode. Recently, some authors have performed studies with different anchorage systems, finding that these systems are able to delay or prevent debonding . Studies include the following anchorage systems: Overlap, embedded bars, shear keys, shear restraint and fiber anchors. Chapter 4 briefly describes several experimental works between years 2000 and 2013, concerning different anchorage systems. The main parameters that measure the anchorage efficiency are: failure mode, failure load increase, displacements (in order to evaluate the ductility of the system); all these data points strongly depend on: reinforcement system, FRP fibers, anchorage system, and also on the specific anchorage parameters. Specific anchorage parameters are a function of the anchorage system used. The embedded bar system have design variables which can be identified as: bar diameter and material, surface finish, groove dimensions, and adhesive. In FRP anchorages (spikes) a complete design characterisation should include: type of fiber, manufacturing process, diameter, fan orientation, anchor splay width, anchor longitudinal spacing and number or rows, number or FRP sheet plies, bonded length beyond anchorage devices,...the parameters considered differ from some authors to others, so the comparison of results is quite complicated. Chapter 5 includes the most common tests used in experimental investigations on bond-behaviour and anchorage characterisation: direct shear tests (with variations single-shear and double-shear), pullout tests and bending tests. Each of them may be used according to the data needed. The purpose of this text is to promote further investigation of anchor spikes, accepting that both FRP anchors and embedded bars are the most versatile anchorage systems of FRP reinforcement and considering that to date its efficiency cannot be evaluated as there are too many design uncertainties.

Dynamics of thermal ignition of spray flames in mixing layers

Conditions are identified under which analyses of laminar mixing layers can shed light on aspects of turbulent spray combustion. With this in mind, laminar spray-combustion models are formulated for both non-premixed and partially premixed systems. The laminar mixing layer separating a hot-air stream from a monodisperse spray carried by either an inert gas or air is investigated numerically and analytically in an effort to increase understanding of the ignition process leading to stabilization of high-speed spray combustion. The problem is formulated in an Eulerian framework, with the conservation equations written in the boundary-layer approximation and with a one-step Arrhenius model adopted for the chemistry description. The numerical integrations unveil two different types of ignition behaviour depending on the fuel availability in the reaction kernel, which in turn depends on the rates of droplet vaporization and fuel-vapour diffusion. When sufficient fuel is available near the hot boundary, as occurs when the thermochemical properties of heptane are employed for the fuel in the integrations, combustion is established through a precipitous temperature increase at a well-defined thermal-runaway location, a phenomenon that is amenable to a theoretical analysis based on activation-energy asymptotics, presented here, following earlier ideas developed in describing unsteady gaseous ignition in mixing layers. By way of contrast, when the amount of fuel vapour reaching the hot boundary is small, as is observed in the computations employing the thermochemical properties of methanol, the incipient chemical reaction gives rise to a slowly developing lean deflagration that consumes the available fuel as it propagates across the mixing layer towards the spray. The flame structure that develops downstream from the ignition point depends on the fuel considered and also on the spray carrier gas, with fuel sprays carried by air displaying either a lean deflagration bounding a region of distributed reaction or a distinct double-flame structure with a rich premixed flame on the spray side and a diffusion flame on the air side. Results are calculated for the distributions of mixture fraction and scalar dissipation rate across the mixing layer that reveal complexities that serve to identify differences between spray-flamelet and gaseous-flamelet problems.

Isolation and one-step preparation of A2E and iso-A2E, fluorophores from human retinal pigment epithelium

Age-related macular degeneration, a major cause of blindness for which no satisfactory treatments exist, leads to a gradual decrease in central high acuity vision. The accumulation of fluorescent materials, called lipofuscin, in retinal pigment epithelial cells of the aging retina is most pronounced in the macula. One of the fluorophores of retinal pigment epithelial lipofuscin has been characterized as A2E, a pyridinium bis-retinoid, which is derived from two molecules of vitamin A aldehyde and one molecule of ethanolamine. An investigation aimed at optimizing the in vitro synthesis of A2E has resulted in the one-step biomimetic preparation of this pigment in 49% yield, readily producing more than 50 mg in one step. These results have allowed for the optimization of HPLC conditions so that nanogram quantities of A2E can be detected from extracts of tissue samples. By using 5% of the extract from individual aged human eyes, this protocol has led to the quantification of A2E and the characterization of iso-A2E, a new A2E double bond isomer; all-trans-retinol and 13-cis-retinol also have been identified in these HPLC chromatograms. Exposure of either A2E or iso-A2E to light gives rise to 4:1 A2E:iso-A2E equilibrium mixtures, similar to the composition of these two pigments in eye extracts. A2E and iso-A2E may exhibit surfactant properties arising from their unique wedge-shaped structures.

Redesign of soluble fatty acid desaturases from plants for altered substrate specificity and double bond position

Acyl-acyl carrier protein (ACP) desaturases introduce double bonds at specific positions in fatty acids of defined chain lengths and are one of the major determinants of the monounsaturated fatty acid composition of vegetable oils. Mutagenesis studies were conducted to determine the structural basis for the substrate and double bond positional specificities displayed by acyl-ACP desaturases. By replacement of specific amino acid residues in a Δ6-palmitoyl (16:0)-ACP desaturase with their equivalents from a Δ9-stearoyl (18:0)-ACP desaturase, mutant enzymes were identified that have altered fatty acid chain-length specificities or that can insert double bonds into either the Δ6 or Δ9 positions of 16:0- and 18:0-ACP. Most notably, by replacement of five amino acids (A181T/A200F/S205N/L206T/G207A), the Δ6-16:0-ACP desaturase was converted into an enzyme that functions principally as a Δ9-18:0-ACP desaturase. Many of the determinants of fatty acid chain-length specificity in these mutants are found in residues that line the substrate binding channel as revealed by x-ray crystallography of the Δ9-18:0-ACP desaturase. The crystallographic model of the active site is also consistent with the diverged activities associated with naturally occurring variant acyl-ACP desaturases. In addition, on the basis of the active-site model, a Δ9-18:0-ACP desaturase was converted into an enzyme with substrate preference for 16:0-ACP by replacement of two residues (L118F/P179I). These results demonstrate the ability to rationally modify acyl-ACP desaturase activities through site-directed mutagenesis and represent a first step toward the design of acyl-ACP desaturases for the production of novel monounsaturated fatty acids in transgenic oilseed crops.

Explanation by the double-metal-ion mechanism of catalysis for the differential metal ion effects on the cleavage rates of 5′-oxy and 5′-thio substrates by a hammerhead ribozyme

In a previous examination using natural all-RNA substrates that contained either a 5′-oxy or 5′-thio leaving group at the cleavage site, we demonstrated that (i) the attack by the 2′-oxygen at C17 on the phosphorus atom is the rate-limiting step only for the substrate that contains a 5′-thio group (R11S) and (ii) the departure of the 5′ leaving group is the rate-limiting step for the natural all-RNA substrate (R11O) in both nonenzymatic and hammerhead ribozyme-catalyzed reactions; the energy diagrams for these reactions were provided in our previous publication. In this report we found that the rate of cleavage of R11O by a hammerhead ribozyme was enhanced 14-fold when Mg2+ ions were replaced by Mn2+ ions, whereas the rate of cleavage of R11S was enhanced only 2.2-fold when Mg2+ ions were replaced by Mn2+ ions. This result appears to be exactly the opposite of that predicted from the direct coordination of the metal ion with the leaving 5′-oxygen, because a switch in metal ion specificity was not observed with the 5′-thio substrate. However, our quantitative analyses based on the previously provided energy diagram indicate that this result is in accord with the double-metal-ion mechanism of catalysis.

A Double-Strand Break Repair Component Is Essential for S Phase Completion in Fission Yeast Cell Cycling

Fission yeast rad22+, a homologue of budding yeast RAD52, encodes a double-strand break repair component, which is dispensable for proliferation. We, however, have recently obtained a cell division cycle mutant with a temperature-sensitive allele of rad22+, designated rad22-H6, which resulted from a point mutation in the conserved coding sequence leading to one amino acid alteration. We have subsequently isolated rad22+ and its novel homologue rti1+ as multicopy suppressors of this mutant. rti1+ suppresses all the defects of cells lacking rad22+. Mating type switch-inactive heterothallic cells lacking either rad22+ or rti1+ are viable, but those lacking both genes are inviable and arrest proliferation with a cell division cycle phenotype. At the nonpermissive temperature, a synchronous culture of rad22-H6 cells performs DNA synthesis without delay and arrests with chromosomes seemingly intact and replication completed and with a high level of tyrosine-phosphorylated Cdc2. However, rad22-H6 cells show a typical S phase arrest phenotype if combined with the rad1-1 checkpoint mutation. rad22+ genetically interacts with rad11+, which encodes the large subunit of replication protein A. Deletion of rad22+/rti1+ or the presence of rad22-H6 mutation decreases the restriction temperature of rad11-A1 cells by 4–6°C and leads to cell cycle arrest with chromosomes incompletely replicated. Thus, in fission yeast a double-strand break repair component is required for a certain step of chromosome replication unlinked to repair, partly via interacting with replication protein A.

Specific Sterols Required for the Internalization Step of Endocytosis in Yeast

Sterols are major components of the plasma membrane, but their functions in this membrane are not well understood. We isolated a mutant defective in the internalization step of endocytosis in a gene (ERG2) encoding a C-8 sterol isomerase that acts in the late part of the ergosterol biosynthetic pathway. In the absence of Erg2p, yeast cells accumulate sterols structurally different from ergosterol, which is the major sterol in wild-type yeast. To investigate the structural requirements of ergosterol for endocytosis in more detail, several erg mutants (erg2Δ, erg6Δ, and erg2Δerg6Δ) were made. Analysis of fluid phase and receptor-mediated endocytosis indicates that changes in the sterol composition lead to a defect in the internalization step. Vesicle formation and fusion along the secretory pathway were not strongly affected in the ergΔ mutants. The severity of the endocytic defect correlates with changes in sterol structure and with the abundance of specific sterols in the ergΔ mutants. Desaturation of the B ring of the sterol molecules is important for the internalization step. A single desaturation at C-8,9 was not sufficient to support internalization at 37°C whereas two double bonds, either at C-5,6 and C-7,8 or at C-5,6 and C-8,9, allowed internalization.

Covalent protein-DNA complexes at the 5' strand termini of meiosis-specific double-strand breaks in yeast.

During meiosis in Saccharomyces cerevisiae, the first chemical step in homologous recombination is the occurrence of site-specific DNA double-strand breaks (DSBs). In wild-type cells, these breaks undergo resection of their 5' strand termini to yield molecules with 3' single-stranded tails. We have further characterized the breaks that accumulate in rad50S mutant stains defective in DSB resection. We find that these DSBs are tightly associated with protein via what appears to be a covalent linkage. When genomic DNA is prepared from meiotic rad50S cultures without protease treatment steps, the restriction fragments diagnostic of DSBs selectively partition to the organic-aqueous interphase in phenol extractions and band at lower than normal density in CsCl density gradients. Selective partitioning and decreased buoyant density are abolished if the DNA is treated with proteinase K prior to analysis. Similar results are obtained with sae2-1 mutant strains, which have phenotypes identical to rad50S mutants. The protein is bound specifically to the 5' strand termini of DSBs and is present at both 5' ends in at least a fraction of breaks. The stability of the complex to various protein denaturants and the strand specificity of the attachment are most consistent with a covalent linkage to DSB termini. We propose that the DSB-associated protein is the catalytic subunit of the meiotic recombination initiation nuclease and that it cleaves DNA via a covalent protein-DNA intermediate.

Characterization of immature thymocyte lines derived from T-cell receptor or recombination activating gene 1 and p53 double mutant mice.

The T-cell receptor (TCR) beta chain is instrumental in the progression of thymocyte differentiation from the CD4-CD8- to the CD4+CD8+ stage. This differentiation step may involve cell surface expression of novel CD3-TCR complexes. To facilitate biochemical characterization of these complexes, we established cell lines from thymic lymphomas originating from mice carrying a mutation in the p53 gene on the one hand and a mutation in TCR-alpha, TCR-beta, or the recombination activating gene 1 (RAG-1) on the other hand. The cell lines were CD4+CD8+ and appeared to be monoclonal. A cell line derived from a RAG-1 x p53 double mutant thymic lymphoma expressed low levels of CD3-epsilon, -gamma, and -delta on the surface. TCR-alpha x p53 double mutant cell lines were found to express complexes consisting of TCR-beta chains associated with CD3-epsilon, -gamma, and -delta chains and CD3-zeta zeta dimers. These lines will be useful tools to study the molecular structure and signal transducing properties of partial CD3-TCR complexes expressed on the surface of immature thymocytes.

The Single Supervisory Mechanism: A Sound First Step in Europe’s Banking Union? Egmont European Affairs Paper, March 2013

The financial and economic crisis has hit Europe in its core. While the crisis may not have originated in the European Union, it has laid bare structural weaknesses in the EU’s policy framework. Both public finances and the banking sector have been heavily affected. For a long time, the EU failed to take into account sufficiently the perverse link that existed between the two. Negative evolutions in one field of the crisis often dragged along the other in its downward spiral. In June 2012, in the early hours of a yet another EU Summit, the leaders of the eurozone finally decided to address the link between the banking and sovereign debt crises. Faced with soaring public borrowing costs in Spain and Italy, they decided to allow for the direct European recapitalisation of banks when the Member State itself would no longer be in a position to do so. In exchange, supervision of the banking sector would be lifted to the European level by means of a Single Supervisory Mechanism. The Single Supervisory Mechanism, or SSM in the EU jargon, is a first step in the broader revision of policies towards banks in Europe. The eventual goal is the creation of a Banking Union, which is to carry out effective surveillance and – if needed – crisis management of the banking sector. The SSM is to rely on national supervisors and the ECB, with the ECB having final authority on the matter. The involvement of the latter made it clear that the SSM would be centred on the eurozone – while it is to remain open to other Member States willing to join. Due to the ongoing problems and the link between the creation of the SSM and the recapitalisation of banks, the SSM became one of the key legislative priorities of the EU. In December 2012, Member States reached an agreement on the design of the SSM. After discussions with the European Parliament (which were still ongoing at the time of writing), the process towards making the SSM operational can be initiated. The goal is to have the SSM fully up and running in the first half of 2014. The decisions that were taken in June 2012 are likely to have had a bigger impact than the eurozone’s Heads of State and Government could have realised at the time for two important reasons. On the one hand, creating the SSM necessitates a full Banking Union and therefore shared risk. On the other hand, the decisions improved the ECB’s perception of the willingness of governments to take far-reaching measures. This undoubtedly played a significant role in the creation of the Outright Monetary Transactions programme by the ECB, which has led to a substantial easing of the crisis in the short-term. 1 These short-term gains should now be matched with a stable long-term framework for bank supervision and crisis management. The agreement on the SSM should be the first step in the direction of this goal. This paper provides an analysis of the SSM and its role in the creation of a Banking Union. The paper starts with a reminder of why the EU decided to put in place the SSM (§1) and the state of play of the ongoing negotiations on the SSM (§2). Subsequently, the supervisory responsibilities of the SSM are detailed, including its scope and the division of labour between the national supervisors and the ECB (§3). The internal functioning of the SSM (§4) and its relation to the other supervisors are discussed afterwards (§5). As mentioned earlier, the SSM is part of a wider move towards a Banking Union. Therefore, this paper sheds light on the other building blocks of this ambitious project (§6). The transition towards the Banking Union is important and will prove to be a bumpy ride. Before formulating a number of conclusions, this Working Paper therefore provides an overview of the planned road ahead (§7).

Coral mortality increases wave energy reaching shores protected by reef flats: Examples from the Seychelles

In the granitic Seychelles, many shores and beaches are fringed by coral reef flats which provide protection to shores from erosion by waves. The surfaces of these reef flats support a complex ecology. About 10 years ago their seaward zones were extensively covered by a rich coral growth, which reached approximately to mean low water level, but in 1998 this was largely killed by seawater warming. The resulting large expanses of dead coral skeletons in these locations are now disintegrating, and much of the subsequent modest recovery by new coral recruitment was set back by further mortalities. A mathematical model of wave energy reaching shorelines protected by coral reef flats has been applied to 14 Seychelles reefs. It is derived from equations which predict: (1) the raised water level, or wave set-up, on reef flats resulting from wave breaking, which depends upon offshore wave height and period, depth of still water over the reef flat and the reef crest profile, and (2) the decay of energy from reef edge to shoreline that is affected by width of reef flat, surface roughness, sea level rise and 'pseudo-sea level rise' created by increased depth resulting from disintegration of coral colonies. The model treats each reef as one entity, but because biota and zonation on reef flats are not homogenous, all reefs are divided into four zones. In each, cover by both living and dead biota was estimated for calculation of parameters, and then averaged to obtain input data for the model. All possible biological factors were taken into account, such as the ability of seagrass beds to grow upwards to match expected sea level rise, reduction in height of the reef flat in relation to sea level as zones of dead corals decay, and the observed 'rounding' of reef crests as erosion removes corals from those areas. Estimates were also made of all these factors for a time approximately a decade ago, representing a time before the mass coral mortality, and for approximately a decade in the future when the observed rapid state of dead coral colony disintegration is assumed to have reached an end point. Results of increased energy over the past decade explain observations of erosion in some sites in the Seychelles. Most importantly, it is estimated that the rise in energy reaching shores protected by fringing reefs will now accelerate more rapidly, such that the increase expected over the next decade will be approximately double than that seen over the past decade. (c) 2005 Elsevier Ltd. All rights reserved.

British Double Agents and Operation Fortitude: A New Perspective

On June 6th, 1944, Allied forces stormed the beaches of Normandy as a part of Operation Overlord, the Allied invasion of France. While they experienced pockets of stiff resistance, Allied troops sustained far fewer casualties than they had expected. The reason for this was due to Operation Fortitude, a deception mission that intended to fool Hitler about the time and location of the Allied invasion mission. The use of double agents by British Intelligence services was essential for the effective execution of Fortitude. The story of the double agents goes beyond their success during Fortitude. Double agents were initially recruited as German agents, but key agents immediately turned themselves in to British authorities upon reaching the nation. These agents decided to become involved with British Intelligence due to broader circumstances that were happening in Europe. The emergence of Fascist regimes disrupted the political landscape of Europe and led to widespread condemnation from political and social spheres. Their development as double agents became crucial to their effectiveness during Operation Fortitude. Their successful infiltration of German Intelligence allowed them to convince Hitler and German High Command that the main Allied invasion force would come at the Pas de Calais instead of Normandy. The result was that the Allies met an unprepared German defense force on D-Day and were able to advance past the beaches. The work of the double agents during Fortitude saved thousands of Allied lives and was vital to the success of Operation Overlord.

Vibrational spectroscopy of phthalocyanine and naphthalocyanine in sandwich-type (na)phthalocyaninato and porphyrinato rare earth complexes: Part 14. The infrared and Raman characteristics of phthalocyanine in “pinwheel-like” homoleptic bis[1,8,15,22-tetrakis(3-pentyloxy)phthalocyaninato] rare earth(III) double-decker complexes

The infrared (IR) spectroscopic data and Raman spectroscopic properties for a series of 13 “pinwheel-like” homoleptic bis(phthalocyaninato) rare earth complexes M[Pc(α-OC5H11)4]2 [M = Y and Pr–Lu except Pm; H2Pc(α-OC5H11)4 = 1,8,15,22-tetrakis(3-pentyloxy)phthalocyanine] have been collected and comparatively studied. Both the IR and Raman spectra for M[Pc(α-OC5H11)4]2 are more complicated than those of homoleptic bis(phthalocyaninato) rare earth analogues, namely M(Pc)2 and M[Pc(OC8H17)8]2, but resemble (for IR) or are a bit more complicated (for Raman) than those of heteroleptic counterparts M(Pc)[Pc(α-OC5H11)4], revealing the decreased molecular symmetry of these double-decker compounds, namely S8. Except for the obvious splitting of the isoindole breathing band at 1110–1123 cm−1, the IR spectra of M[Pc(α-OC5H11)4]2 are quite similar to those of corresponding M(Pc)[Pc(α-OC5H11)4] and therefore are similarly assigned. With laser excitation at 633 nm, Raman bands derived from isoindole ring and aza stretchings in the range of 1300–1600 cm−1 are selectively intensified. The IR spectra reveal that the frequencies of pyrrole stretching and pyrrole stretching coupled with the symmetrical CH bending of –CH3 groups are sensitive to the rare earth ionic size, while the Raman technique shows that the bands due to the isoindole stretchings and the coupled pyrrole and aza stretchings are similarly affected. Nevertheless, the phthalocyanine monoanion radical Pc′− IR marker band of bis(phthalocyaninato) complexes involving the same rare earth ion is found to shift to lower energy in the order M(Pc)2 > M(Pc)[Pc(α-OC5H11)4] > M[Pc(α-OC5H11)4]2, revealing the weakened π–π interaction between the two phthalocyanine rings in the same order.

Tuning the valence of the cerium center in (Na)phthalocyaninato and porphyrinato cerium double-deckers by changing the nature of the tetrapyrrole ligands

A series of 7 cerium double-decker complexes with various tetrapyrrole ligands including porphyrinates, phthalocyaninates, and 2,3-naphthalocyaninates have been prepared by previously described methodologies and characterized with elemental analysis and a range of spectroscopic methods. The molecular structures of two heteroleptic \[(na)phthalocyaninato](porphyrinato) complexes have also been determined by X-ray diffraction analysis which exhibit a slightly distorted square antiprismatic geometry with two domed ligands. Having a range of tetrapyrrole ligands with very different electronic properties, these compounds have been systematically investigated for the effects of ligands on the valence of the cerium center. On the basis of the spectroscopic (UV−vis, near-IR, IR, and Raman), electrochemical, and structural data of these compounds and compared with those of the other rare earth(III) counterparts reported earlier, it has been found that the cerium center adopts an intermediate valence in these complexes. It assumes a virtually trivalent state in cerium bis(tetra-tert-butylnaphthalocyaninate) as a result of the two electron rich naphthalocyaninato ligands, which facilitate the delocalization of electron from the ligands to the metal center. For the rest of the cerium double-deckers, the cerium center is predominantly tetravalent. The valences (3.59−3.68) have been quantified according to their LIII-edge X-ray absorption near-edge structure (XANES) profiles.