The COP9 signalosome counteracts the accumulation of cullin SCF ubiquitin E3 RING ligases during fungal development

Defects in the COP9 signalosome (CSN) impair multicellular development, including embryonic plant or animal death or a block in sexual development of the fungus Aspergillus nidulans. CSN deneddylates cullin-RING ligases (CRLs), which are activated by covalent linkage to ubiquitin-like NEDD8. Deneddylation allows CRL disassembly for subsequent reassembly. An attractive hypothesis is a consecutive order of CRLs for development, which demands repeated cycles of neddylation and deneddylation for reassembling CRLs. Interruption of these cycles could explain developmental blocks caused by csn mutations. This predicts an accumulation of neddylated CRLs exhibiting developmental functions when CSN is dysfunctional. We tested this hypothesis in A. nidulans, which tolerates reduced levels of neddylation for growth. We show that only genes for CRL subunits or neddylation are essential, whereas CSN is primarily required for development. We used functional tagged NEDD8, recruiting all three fungal cullins. Cullins are associated with the CSN1/CsnA subunit when deneddylation is defective. Two CRLs were identified which are specifically involved in differentiation and accumulate during the developmental block. This suggests that an active CSN complex is required to counteract the accumulation of specific CRLs during development.

Regioregular improvement on the oxidative polymerization of poly-3-octylthiophenes by slow addition of oxidant at low temperature

Many pathways can be used to synthesize polythiophenes derivatives. The polycondensation reactions performed with organometallics are preferred since they lead to regioregular polymers (with high content of heat-to-tail coupling) which have enhanced conductivity and luminescence. However, these pathways have several steps; the reactants are highly moisture sensitive and expensive. On the other hand, the oxidative polymerization using FeCl3 is a one-pot reaction that requires less moisture sensitive reactants with lower cost, although the most common reaction conditions lead to polymers with low regioregularity. Here, we report that by changing the reaction conditions, such as FeCl3 addition rate and reaction temperature, poly-3-octylthiophenes with different the regioregularities can be obtained, reaching about 80% of heat-to-tail coupling. Different molar mass distributions and polydispersivities were obtained. The preliminary results suggest that the oxidative polymerization process could be improved to yield polythiophenes with higher regioregularity degree and narrower molar mass distributions by just setting some reaction conditions. We also verified that it is possible to solvent extract part of the lower regioregular fraction of the polymer further improving the regioregularity degree. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Solar-Terrestrial Signal Record in Tree Ring Width Time Series from Brazil

This work investigates the behavior of the sunspot number and Southern Oscillation Index (SOI) signal recorded in the tree ring time series for three different locations in Brazil: Humaita in Amaznia State, Porto Ferreira in So Paulo State, and Passo Fundo in Rio Grande do Sul State, using wavelet and cross-wavelet analysis techniques. The wavelet spectra of tree ring time series showed signs of 11 and 22 years, possibly related to the solar activity, and periods of 2-8 years, possibly related to El Nio events. The cross-wavelet spectra for all tree ring time series from Brazil present a significant response to the 11-year solar cycle in the time interval between 1921 to after 1981. These tree ring time series still have a response to the second harmonic of the solar cycle (5.5 years), but in different time intervals. The cross-wavelet maps also showed that the relationship between the SOI x tree ring time series is more intense, for oscillation in the range of 4-8 years.

Influence of the base and diluent methacrylate monomers on the polymerization stress and its determinants

The aim of this study was to evaluate the effect of the association between bisphenol-A diglycidyl dimethacrylate (BisGMA) or its ethoxylated version (BisEMA) with diluents derived from the ethylene glycol dimethacrylate (EGDMA), with increasing number of ethylene glycol units (1: EGDMA, 2: DEGDMA, 3: TEGDMA, or 4: TETGDMA), or trimethylol propane trimethacrylate (TMPTMA) or 1,10-decanediol dimethacrylate (D3MA) on polymerization stress, volumetric shrinkage, degree of conversion, maximum rate of polymerization (Rpmax), and elastic modulus of experimental composites. BisGMA containing formulations presented lower shrinkage and stress but higher modulus and Rpmax than those containing BisEMA. TMPTMA presented the lowest stress among all diluents, as a result of lower conversion. EGDMA, DEGDMA, TEGDMA, and TETGDMA presented similar polymerization stress which was higher than the stress presented by D3MA and TMPTMA. D3MA presented similar conversion when copolymerized with both base monomers. The other diluents presented higher conversion when associated with BisEMA. EGDMA showed similar shrinkage compared with DEGDMA and higher than the other diluents. The lower conversion achieved by TMPTMA did not jeopardize its elastic modulus, similar to the other diluents. Despite the similar conversion presented by D3MA in comparison with EGDMA and DEGDMA, its lower elastic modulus may limit its use. Rather than proposing new materials, this study provides a systematic evaluation of off the shelf monomers and their effects on stress development, as highlighted by the analysis of conversion, shrinkage and modulus, to aid the optimization of commercially available materials. (c) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

OPTIMIZATION AND CONTROL OF A CONTINUOUS POLYMERIZATION REACTOR

This work studies the optimization and control of a styrene polymerization reactor. The proposed strategy deals with the case where, because of market conditions and equipment deterioration, the optimal operating point of the continuous reactor is modified significantly along the operation time and the control system has to search for this optimum point, besides keeping the reactor system stable at any possible point. The approach considered here consists of three layers: the Real Time Optimization (RTO), the Model Predictive Control (MPC) and a Target Calculation (TC) that coordinates the communication between the two other layers and guarantees the stability of the whole structure. The proposed algorithm is simulated with the phenomenological model of a styrene polymerization reactor, which has been widely used as a benchmark for process control. The complete optimization structure for the styrene process including disturbances rejection is developed. The simulation results show the robustness of the proposed strategy and the capability to deal with disturbances while the economic objective is optimized.

Peripheral Sterile Corneal Ring Infiltrate After Riboflavin-UVA Collagen Cross-Linking in Keratoconus

Purpose: To present 7 cases of peripheral sterile corneal infiltrates that occurred after corneal cross-linking (CXL) for progressive keratectasia. Methods: Seven patients who had their progressive keratoconus documented underwent corneal deepithelization and subsequently CXL, which was performed with the application of 0.1% riboflavin with 20% dextran, and exposure to UVA light (370 nm, 2.9-3.1 mW/cm(2)) for 30 minutes. Results: Nearly a week after the procedure, the patients presented with peripheral stromal infiltrates. The ring-like infiltrates were superficial and were present at the 9.0-mm zone. Sterile infiltration was diagnosed. Patients were treated with topical corticosteroids, and complete resolution was achieved after a few weeks of treatment. Conclusions: We hypothesize that the phototoxic effect on the corneal stroma may be the main mechanism that triggers these infiltrates. Alternatively, alterations in antigenicity that occur in native proteins after CXL could result in patients recognizing the proteins as nonself and mounting immune responses.

Mechanisms of ring chromosome formation, ring instability and clinical consequences

Background The breakpoints and mechanisms of ring chromosome formation were studied and mapped in 14 patients. Methods Several techniques were performed such as genome-wide array, MLPA (Multiplex Ligation-Dependent Probe Amplification) and FISH (Fluorescent in situ Hybridization). Results The ring chromosomes of patients I to XIV were determined to be, respectively: r(3)(p26.1q29), r(4)(p16.3q35.2), r(10)(p15.3q26.2), r(10)(p15.3q26.13), r(13)(p13q31.1), r(13)(p13q34), r(14)(p13q32.33), r(15)(p13q26.2), r(18)(p11.32q22.2), r(18)(p11.32q21.33), r(18)(p11.21q23), r(22)(p13q13.33), r(22)(p13q13.2), and r(22)(p13q13.2). These rings were found to have been formed by different mechanisms, such as: breaks in both chromosome arms followed by end-to-end reunion (patients IV, VIII, IX, XI, XIII and XIV); a break in one chromosome arm followed by fusion with the subtelomeric region of the other (patients I and II); a break in one chromosome arm followed by fusion with the opposite telomeric region (patients III and X); fusion of two subtelomeric regions (patient VII); and telomere-telomere fusion (patient XII). Thus, the r(14) and one r(22) can be considered complete rings, since there was no loss of relevant genetic material. Two patients (V and VI) with r(13) showed duplication along with terminal deletion of 13q, one of them proved to be inverted, a mechanism known as inv-dup-del. Ring instability was detected by ring loss and secondary aberrations in all but three patients, who presented stable ring chromosomes (II, XIII and XIV). Conclusions We concluded that the clinical phenotype of patients with ring chromosomes may be related with different factors, including gene haploinsufficiency, gene duplications and ring instability. Epigenetic factors due to the circular architecture of ring chromosomes must also be considered, since even complete ring chromosomes can result in phenotypic alterations, as observed in our patients with complete r(14) and r(22).

Influence of apical foramen lateral opening and file size on cemental canal instrumentation

Since instrumentation of the apical foramen has been suggested for cleaning and disinfection of the cemental canal, selection of the file size and position of the apical foramen have challenging steps. This study analyzed the influence of apical foramen lateral opening and file size can exert on cemental canal instrumentation. Thirty-four human maxillary central incisors were divided in two groups: Group 1 (n=17), without flaring, and Group 2 (n=17), with flaring with LA Axxess burs. K-files of increasing diameters were progressively inserted into the canal until binding at the apical foramen was achieved and tips were visible and bonded with ethyl cyanoacrylate adhesive. Roots/files set were cross-sectioned 5 mm from the apex. Apices were examined by scanning electron microscopy at ×140 and digital images were captured. Data were analyzed statistically by Student’s t test and Fisher’s exact test at 5% significance level. SEM micrographs showed that 19 (56%) apical foramina emerged laterally to the root apex, whereas 15 (44%) coincided with it. Significantly more difficulty to reach the apical foramen was noted in Group 2. Results suggest that the larger the foraminal file size, the more difficult the apical foramen instrumentation may be in laterally emerged cemental canals.

Optimization and control of a continuous polymerization reactor

This work studies the optimization and control of a styrene polymerization reactor. The proposed strategy deals with the case where, because of market conditions and equipment deterioration, the optimal operating point of the continuous reactor is modified significantly along the operation time and the control system has to search for this optimum point, besides keeping the reactor system stable at any possible point. The approach considered here consists of three layers: the Real Time Optimization (RTO), the Model Predictive Control (MPC) and a Target Calculation (TC) that coordinates the communication between the two other layers and guarantees the stability of the whole structure. The proposed algorithm is simulated with the phenomenological model of a styrene polymerization reactor, which has been widely used as a benchmark for process control. The complete optimization structure for the styrene process including disturbances rejection is developed. The simulation results show the robustness of the proposed strategy and the capability to deal with disturbances while the economic objective is optimized.

Coastline changes and sedimentation related with the opening of an artificial channel: The Valo Grande Delta, SE Brazil

The role played by human activity in coastline changes indicates a general tendency of retreating coasts, especially deltaic environments, as a result of the recent trend of sea level rise as well as the blockage of the transfer of sediments towards the coast, especially due to the construction of dams. This is particularly important in deltaic environments which are suffering a dramatic loss of area in the last decades. In contrast, in this paper, we report the origin and evolution of an anthropogenic delta, the Valo Grande delta, on the south-eastern Brazilian coast, whose origin is related to the opening of an artificial channel and the diversion of the main flow of the Ribeira de Iguape River. The methodology included the analysis of coastline changes, bathymetry and coring, which was used to determine the sedimentation rates and grain-size changes over time. The results allowed us to recognize the different facies of the anthropogenic delta and to establish its lateral and vertical depositional trends. Despite not being very frequent, anthropogenic deltas represent a favorable environment for the record of natural and anthropogenic changes in historical times and, thus, deserve more attention from researchers of different subjects

A Galactic ring of minimum stellar density near the solar orbit radius

We analyse the secular effects of a long-lived Galactic spiral structure on the stellar orbits with mean radii close to the corotation resonance. By test-particle simulations and different spiral potential models with parameters constrained on observations, we verified the formation of a minimum with amplitude ∼30–40 per cent of the background disc stellar density at corotation. Such a minimum is formed by the secular angular momentum transfer between stars and the spiral density wave on both sides of corotation. We demonstrate that the secular loss (gain) of angular momentum and decrease (increase) of mean orbital radius of stars just inside (outside) corotation can counterbalance the opposite trend of exchange of angular momentum shown by stars orbiting the librational points L4/5 at the corotation circle. Such secular processes actually allow steady spiral waves to promote radial migration across corotation. We propose some pieces of observational evidence for the minimum stellar density in the Galactic disc, such as its direct relation to the minimum in the observed rotation curve of the Galaxy at the radius r ∼ 9 kpc (for R0 = 7.5 kpc), as well as its association with a minimum in the distribution of Galactic radii of a sample of open clusters older than 1Gyr. The closeness of the solar orbit adius to the corotation resonance implies that the solar orbit lies inside a ring of minimum surface density (stellar + gas). This also implies a correction to larger values for the estimated total mass of the Galactic disc, and consequently, a greater contribution of the disc componente to the inner rotation curve of the Galaxy.

Nonlocal asymmetric exclusion process on a ring and conformal invariance

We present a one-dimensional nonlocal hopping model with exclusion on a ring. The model is related to the Raise and Peel growth model. A nonnegative parameter u controls the ratio of the local backwards and nonlocal forwards hopping rates. The phase diagram, and consequently the values of the current, depend on u and the density of particles. In the special case of half-lling and u = 1 the system is conformal invariant and an exact value of the current for any size L of the system is conjectured and checked for large lattice sizes in Monte Carlo simulations. For u > 1 the current has a non-analytic dependence on the density when the latter approaches the half-lling value.

Theoretical and experimental studies on the electronic, optical, and structural properties of poly-pyrrole-2-carboxylic acid films

A theoretical approach is used here to explain experimental results obtained from the electrosynthesis of polypyrrole-2-carboxylic acid (PPY-2-COOH) films in nonaqueous medium. An analysis of the Fukui function (reactivity index) indicates that the monomer (pyrrole-2-carboxylic acid, PY-2-COOH), and dimers and trimers are oxidized in the C4 or C5 positions of the heterocyclic ring of the PY-2-COOH structure. After calculating the heat of formation using semiempirical Austin Model 1 post-Hartree-Fock parameterization for dimer species, both C4 and C5 positions adjacent to the aromatic rings of PPY-2-COOH were considered the most susceptible ones to oxidative coupling reactions. The ZINDO-S/CI semiempirical method was used to simulate the electronic transitions typically seen in the UV-VIS-NIR range in monomer and oligomers with different conjugation lengths. The use of an electrochemical quartz crystal microbalance provides sufficient information to propose a polymerization mechanism of PY-2-COOH based on molecular modeling and experimental results.

Preliminary interpretation of growth ring on the otolith of Boops boops off Gran Canaria (Canary Islands)

Máster en Gestión Sostenible de Recursos Pesqueros

Materiali Politiofenici Otticamente Attivi

Much effort has been devoted in the recent years to the investigation of optically active polythiophenes characterized by the presence of a chiral moiety linked to the 3-position of the aromatic ring. In addition to their potential technological applications as materials for enantioselective electrodes and membranes, chiral poly(thiophene)s offer the possibility of studying the structural changes accompanying the transition from the disordered state by following the variation of their chiroptical properties by circular dichroism (CD). In solution of a good solvent, that kind of polythiophenes doesn’t display any optical activity arising from the presence of dissymmetric conformation of the backbone, as shown by circular dichroism (CD) spectra. When the macromolecules begin to aggregate, as it occurs e.g. by addition of a poor solvent, or lowering the solution temperature, or when the macromolecules are assembled in the solid state as thin films obtained by solution casting or spin coating, significant CD bands are observed in the spectral region related to the electronic absorptions of the aromatic polythiophene chromophore. These CD bands are indicative of a chiral macromolecule arrangement of one prevailing chirality. The synthesis of -substituted polythiophenes can be carried out starting from the corresponding -substituted mono- or oligomeric thiophenic monomers under regioselective or regiospecific conditions in order to minimize or avoid the formation of head-to-head dyads unfavourably affecting the presence of coplanar conformations of thiophene rings as a consequence of steric interactions between the side-chain substituents, both in solution and in the solid state. To this regard, non-symmetrically substituted monomers require therefore to perform the polymerization in the presence of highly demanding catalysts and reaction condition, whereas with symmetrically substituted oligothiophenic monomers containing the -substituents located far apart from the reacting sites, it is instead possible to obtain regioregular macromolecules by adopting more simple and economic polymerization methods, such as, e. g., the chemical oxidative polymerization with iron (III) trichloride. In order to verify how the polymer structure affects its optical activity, further poly-3-alkylthiophenes, substituted by an enantiomerically pure chiral alkyl group, namely poli[3,3”-di[2((S)-(+)-2-methylbutoxy)ethyl]-2,2’:5’,2”-terthiophene] (PDMBOETT), poli[3,3’di[2((S)-(+)-2-methylbutoxy)ethyl]-2,2’-bitiofene] (PDMBOEBT), poli[3,3””-didodecyl-4’,3”’-di(S)-(+)-2-methylbutyl-2,2’:5’,2”:5”,2”’:5”’,2””-quinquethiophene (PDDDMBQT) have been synthesized and characterized by instrumental techniques. The spectroscopic behaviour of thin films of poly(DDDMBQT) has been investigated in the solid state under different sample preparation procedures. It was also compared with the behaviour of polymers previously made. The experimental results are interpreted in terms of influence of the side-chain substituents on the extent of planarity of the polymeric chains and the formation of optically active chiral aggregates. In recent years conjugated block copolymers have received considerable attention. It is well known that conjugated block copolymers composed of two electronically different blocks can have morphologic and optical properties, that differ from those of their homopolymers. A recent study has also shown that the electronic properties and the supramolecular organization of one conjugated block can also be influenced by the other block. In order to study better this behavior, a new conjugated block copolymers, composed of a regioregular hydrophylic block and a regioregular hydrophobic block namely poli[3[2-(2-metossietossi)etossi]metiltiofene]-co- poli[3(1-octilossi)tiofene], has been synthesized and characterized.