Synthetic applications of intramolecular aza-Wittig reaction for the preparation of heterocyclic compound

[EN] A review focused on recent advances in intramolecular aza-Wittig reaction of phosphazenes with several carbonyl or analogous compounds is reported. Phosphazenes afford intramolecular aza-Wittig reaction with different groups within the molecule as aldehydes, ketones, esters, thioesters, amides, anhydrides and sulfimides. One of the most important applications of this reaction is the synthesis of a wide range of heterocyclic compounds, ranging from simple monocyclic compounds to complex polycyclic and macrocyclic systems.

Las residencias señoriales bajomedievales en el País Vasco: análisis de la evolución del sistema constructivo y sus elementos singulares

8 pag.

Prevalence and magnitude of body weight and image dissatisfaction among women in dietetics majors

[EN] Some authors have suggested that body weight dissatisfaction may be high in students majoring in dietetics. Therefore, this study was conducted to examine the extent of body weight and image dissatisfaction in a sample of women in dietetics major. Additionally, predictors of magnitude of body weight dissatisfaction were analyzed. Participants were 62 volunteers with normalweight whose mean age was 21.87±1.89 years old (nonrandom sample). The assessment instruments included anthropometric measurements, a somatomorphic matrix test and an eating disorders inventory (EDI-2). Data were analyzed using SPSS vs. 15.0. A larger proportion of students chose an ideal body weight lower than actual weight (67.7%) and body image with less body fat and more muscle mass than actual values (56.4%). The magnitude of body weight dissatisfaction was associated with muscle mass and body fat dissatisfaction, and with the subscale of EDI-2 “body dissatisfaction”. So, from a public health standpoint, we consider important to continue working in this line of research with the aim of better understanding the extent of body weight dissatisfaction in women dietitians, and how this dissatisfaction could interfere with their professional practice.

Completions of epsilon-dense partial Latin squares

A classical question in combinatorics is the following: given a partial Latin square $P$, when can we complete $P$ to a Latin square $L$? In this paper, we investigate the class of textbf{$epsilon$-dense partial Latin squares}: partial Latin squares in which each symbol, row, and column contains no more than $epsilon n$-many nonblank cells. Based on a conjecture of Nash-Williams, Daykin and H"aggkvist conjectured that all $frac{1}{4}$-dense partial Latin squares are completable. In this paper, we will discuss the proof methods and results used in previous attempts to resolve this conjecture, introduce a novel technique derived from a paper by Jacobson and Matthews on generating random Latin squares, and use this novel technique to study $ epsilon$-dense partial Latin squares that contain no more than $delta n^2$ filled cells in total.

In Chapter 2, we construct completions for all $ epsilon$-dense partial Latin squares containing no more than $delta n^2$ filled cells in total, given that $epsilon < frac{1}{12}, delta < frac{ left(1-12epsilonright)^{2}}{10409}$. In particular, we show that all $9.8 cdot 10^{-5}$-dense partial Latin squares are completable. In Chapter 4, we augment these results by roughly a factor of two using some probabilistic techniques. These results improve prior work by Gustavsson, which required $epsilon = delta leq 10^{-7}$, as well as Chetwynd and H"aggkvist, which required $epsilon = delta = 10^{-5}$, $n$ even and greater than $10^7$.

If we omit the probabilistic techniques noted above, we further show that such completions can always be found in polynomial time. This contrasts a result of Colbourn, which states that completing arbitrary partial Latin squares is an NP-complete task. In Chapter 3, we strengthen Colbourn's result to the claim that completing an arbitrary $left(frac{1}{2} + epsilonright)$-dense partial Latin square is NP-complete, for any $epsilon > 0$.

Colbourn's result hinges heavily on a connection between triangulations of tripartite graphs and Latin squares. Motivated by this, we use our results on Latin squares to prove that any tripartite graph $G = (V_1, V_2, V_3)$ such that begin{itemize} item $|V_1| = |V_2| = |V_3| = n$, item For every vertex $v in V_i$, $deg_+(v) = deg_-(v) geq (1- epsilon)n,$ and item $|E(G)| > (1 - delta)cdot 3n^2$ end{itemize} admits a triangulation, if $epsilon < frac{1}{132}$, $delta < frac{(1 -132epsilon)^2 }{83272}$. In particular, this holds when $epsilon = delta=1.197 cdot 10^{-5}$.

This strengthens results of Gustavsson, which requires $epsilon = delta = 10^{-7}$.

In an unrelated vein, Chapter 6 explores the class of textbf{quasirandom graphs}, a notion first introduced by Chung, Graham and Wilson cite{chung1989quasi} in 1989. Roughly speaking, a sequence of graphs is called "quasirandom"' if it has a number of properties possessed by the random graph, all of which turn out to be equivalent. In this chapter, we study possible extensions of these results to random $k$-edge colorings, and create an analogue of Chung, Graham and Wilson's result for such colorings.

高频可变间距全息光栅的制作方法的计算机模拟研究

提出了一种制作高频线性可变频率光栅的新方法，并给出了光栅空间频率的表达式．通过在相干的两光路中插入特殊透镜，可以实现线性可变空间频率光栅的制作，而且通过适当地调节实验参数可以改变空间频率的变化率．给出了相应的模拟全息图。

Ground-state energy shifts of H-like Ti under dense and hot plasma conditions

In this study, by adopting the ion sphere model, the self-consistent. field method is used with the Poisson-Boltzmann equation and the Dirac equation to calculate the ground-state energies of H-like Ti at a plasma electron density from 10(22) cm(-3) to 10(24) cm(-3) and the electron temperature from 100 eV to 3600 eV. The ground-state energy shifts of H-like Ti show different trends with the electron density and the electron temperature. It is shown that the energy shifts increase with the increase in the electron density and decrease with the increase in the electron temperature. The energy shifts are sensitive to the electron density, but only sensitive to the low electron temperature. In addition, an accurately fitting formula is obtained to fast estimate the ground-state energies of H-like Ti. Such fitted formula can also be used to estimate the critical electron density of pressure ionization for the ground state of H-like Ti.

Ari progresiboaz: euskararen kasu markak

Pablo Albizu eta Beatriz Fernández (arg.)

Nuclear Energy Levels of ^31S and ^33Cl

The reaction ³²S(³He, α) ³¹S has been used to locate 42 levels in ³¹S. For 11 of the first 17 levels ℓ_n-values have been determined. The first 6 excited states of ³¹S have been studied by applying the particle-gamma correlation method of Litherland and Ferguson (their Method II) to the reaction ³²S(³He, αγ) ³¹S. The resulting spins and parities are: E_X, J^π = 1.25 MeV, 3/2⁺; 2.23 MeV, 5/2⁺; 3.08 MeV, 1/2⁺; 3.29 MeV, 5/2⁺, 3/2⁺; 3.35 MeV, 7/2, 3/2; 3.44 MeV, 3/2⁺. Mixing and branching ratios have also been determined. The ground state Q-value for the reaction ³²S(³He, α)³¹S has been measured to be 5.538 ± 0.006 MeV. Analysis of the spectra of the reaction ³²S(³He, α)³³Cl which were obtained as a by-product of the spectra of the reaction ³²S(³He, α) ³¹S located levels in ³³Cl at the following excitation energies: 0, 810 ± 9, (1978 ± 14), 2351 ± 9, 2686 ± 8, 2848 ± 9 (a known doublet), 2980 ± 9, and 4119 ± 10 keV. The 2.0 MeV level was only weakly populated, and to confirm its existence the reaction ³⁶Ar(p, α)³³Cl has been studied. In this reaction the 2.0 MeV level was strongly populated and the measured excitation energy was 1999 ± 20 keV. The experimental results for ³¹S and ³³Cl are compared with their analogs and with nuclear model predictions.

长周期光纤光栅波导色散因子和有效折射率热光系数的测量

对串联的长周期光纤光栅(CLPFG)的透射谱特性进行了理论分析和实验研究。分析表明，长周期光纤光栅中纤芯模和包层模之间的马赫-曾德尔干涉效应导致在长周期光纤光栅谐振峰内的梳状滤波结构特性；其峰值位置和峰间距同串联区光纤的长度以及光纤的波导色散因子有关。测量了长周期光纤光栅的透射谱，并研究了其温度特性。根据测量数据，得到对应于1554nm波长处，所用单模光纤HE14模的波导色散因子γ为0．874；纤芯／包层有效折射率差的热光系数为4．8×10^-5℃^-1。并对这一测试方法和结果，以及长周期光纤光栅的应用进

Investigations of DNA-mediated protein oxidation

DNA charge transport (CT) involves the efficient transfer of electrons or electron holes through the DNA π-stack over long molecular distances of at least 100 base-pairs. Despite this shallow distance dependence, DNA CT is sensitive to mismatches or lesions that disrupt π-stacking and is critically dependent on proper electronic coupling of the donor and acceptor moieties into the base stack. Favorable DNA CT is very rapid, occurring on the picosecond timescale. Because of this speed, electron holes equilibrate along the DNA π-stack, forming a characteristic pattern of DNA damage at low oxidation potential guanine multiplets. Furthermore, DNA CT may be used in a biological context. DNA processing enzymes with 4Fe4S clusters can perform DNA-mediated electron transfer (ET) self-exchange reactions with other 4Fe4S cluster proteins, even if the proteins are quite dissimilar, as long as the DNA-bound [4Fe4S]^3+/2+ redox potentials are conserved. This mechanism would allow low copy number DNA repair proteins to find their lesions efficiently within the cell. DNA CT may also be used biologically for the long-range, selective activation of redox-active transcription factors. Within this work, we pursue other proteins that may utilize DNA CT within the cell and further elucidate aspects of the DNA-mediated ET self-exchange reaction of 4Fe4S cluster proteins.

Dps proteins, bacterial mini-ferritins that protect DNA from oxidative stress, are implicated in the survival and virulence of pathogenic bacteria. One aspect of their protection involves ferroxidase activity, whereby ferrous iron is bound and oxidized selectively by hydrogen peroxide, thereby preventing formation of damaging hydroxyl radicals via Fenton chemistry. Understanding the specific mechanism by which Dps proteins protect the bacterial genome could inform the development of new antibiotics. We investigate whether DNA-binding E. coli Dps can utilize DNA CT to protect the genome from a distance. An intercalating ruthenium photooxidant was employed to generate oxidative DNA damage via the flash-quench technique, which localizes to a low potential guanine triplet. We find that Dps loaded with ferrous iron, in contrast to Apo-Dps and ferric iron-loaded Dps which lack available reducing equivalents, significantly attenuates the yield of oxidative DNA damage at the guanine triplet. These data demonstrate that ferrous iron-loaded Dps is selectively oxidized to fill guanine radical holes, thereby restoring the integrity of the DNA. Luminescence studies indicate no direct interaction between the ruthenium photooxidant and Dps, supporting the DNA-mediated oxidation of ferrous iron-loaded Dps. Thus DNA CT may be a mechanism by which Dps efficiently protects the genome of pathogenic bacteria from a distance.

Further work focused on spectroscopic characterization of the DNA-mediated oxidation of ferrous iron-loaded Dps. X-band EPR was used to monitor the oxidation of DNA-bound Dps after DNA photooxidation via the flash-quench technique. Upon irradiation with poly(dGdC)₂, a signal arises with g = 4.3, consistent with the formation of mononuclear high-spin Fe(III) sites of low symmetry, the expected oxidation product of Dps with one iron bound at each ferroxidase site. When poly(dGdC)₂ is substituted with poly(dAdT)₂, the yield of Dps oxidation is decreased significantly, indicating that guanine radicals facilitate Dps oxidation. The more favorable oxidation of Dps by guanine radicals supports the feasibility of a long-distance protection mechanism via DNA CT where Dps is oxidized to fill guanine radical holes in the bacterial genome produced by reactive oxygen species.

We have also explored possible electron transfer intermediates in the DNA-mediated oxidation of ferrous iron-loaded Dps. Dps proteins contain a conserved tryptophan residue in close proximity to the ferroxidase site (W52 in E. coli Dps). In comparison to WT Dps, in EPR studies of the oxidation of ferrous iron-loaded Dps following DNA photooxidation, W52Y and W52A mutants were deficient in forming the characteristic EPR signal at g = 4.3, with a larger deficiency for W52A compared to W52Y. In addition to EPR, we also probed the role of W52 Dps in cells using a hydrogen peroxide survival assay. Bacteria containing W52Y Dps survived the hydrogen peroxide challenge more similarly to those containing WT Dps, whereas cells with W52A Dps died off as quickly as cells without Dps. Overall, these results suggest the possibility of W52 as a CT hopping intermediate.

DNA-modified electrodes have become an essential tool for the study of the redox chemistry of DNA processing enzymes with 4Fe4S clusters. In many cases, it is necessary to investigate different complex samples and substrates in parallel in order to elucidate this chemistry. Therefore, we optimized and characterized a multiplexed electrochemical platform with the 4Fe4S cluster base excision repair glycosylase Endonuclease III (EndoIII). Closely packed DNA films, where the protein has limited surface accessibility, produce EndoIII electrochemical signals sensitive to an intervening mismatch, indicating a DNA-mediated process. Multiplexed analysis allowed more robust characterization of the CT-deficient Y82A EndoIII mutant, as well as comparison of a new family of mutations altering the electrostatics surrounding the 4Fe4S cluster in an effort to shift the reduction potential of the cluster. While little change in the DNA-bound midpoint potential was found for this family of mutants, likely indicating the dominant effect of DNA-binding on establishing the protein redox potential, significant variations in the efficiency of DNA-mediated electron transfer were apparent. On the basis of the stability of these proteins, examined by circular dichroism, we proposed that the electron transfer pathway in EndoIII can be perturbed not only by the removal of aromatic residues but also through changes in solvation near the cluster.

While the 4Fe4S cluster of EndoIII is relatively insensitive to oxidation and reduction in solution, we have found that upon DNA binding, the reduction potential of the [4Fe4S]^3+/2+ couple shifts negatively by approximately 200 mV, bringing this couple into a physiologically relevant range. Demonstrated using electrochemistry experiments in the presence and absence of DNA, these studies do not provide direct molecular evidence for the species being observed. Sulfur K-edge X-ray absorbance spectroscopy (XAS) can be used to probe directly the covalency of iron-sulfur clusters, which is correlated to their reduction potential. We have shown that the Fe-S covalency of the 4Fe4S cluster of EndoIII increases upon DNA binding, stabilizing the oxidized [4Fe4S]³⁺ cluster, consistent with a negative shift in reduction potential. The 7% increase in Fe-S covalency corresponds to an approximately 150 mV shift, remarkably similar to DNA electrochemistry results. Therefore we have obtained direct molecular evidence for the shift in 4Fe4S reduction potential of EndoIII upon DNA binding, supporting the feasibility of our model whereby these proteins can utilize DNA CT to cooperate in order to efficiently find DNA lesions inside cells.

In conclusion, in this work we have explored the biological applications of DNA CT. We discovered that the DNA-binding bacterial ferritin Dps can protect the bacterial genome from a distance via DNA CT, perhaps contributing to pathogen survival and virulence. Furthermore, we optimized a multiplexed electrochemical platform for the study of the redox chemistry of DNA-bound 4Fe4S cluster proteins. Finally, we have used sulfur K-edge XAS to obtain direct molecular evidence for the negative shift in 4Fe4S cluster reduction potential of EndoIII upon DNA binding. These studies contribute to the understanding of DNA-mediated protein oxidation within cells.

Estratégia para validação de processos de esterilização por vapor saturado em autoclaves nas indústrias farmacêuticas

O objetivo deste trabalho foi criar uma metodologia de validação e revalidação dos processos de esterilização por calor úmido em autoclaves horizontais, destacando os pontos críticos do processo e concentrando esforços onde são realmente necessários. Foram realizados estudos de distribuição térmica, de penetração de calor e de desafio microbiológico na validação da autoclave STERIS FINNAQUA 6912. Com o objetivo de avaliar o impacto de uma mudança e compreender a relação entre os fatores e suas interações para o processo de esterilização, foi utilizado o planejamento fatorial 23 dos fatores densidade da carga (quantidade de itens), embalagem do produto e localização na câmara interna. Os estudos de distribuição térmica confirmaram a distribuição homogênea de calor na câmara interna durante o tempo de exposição a 121C. As temperaturas variaram entre 120,35C e 120,92C com desvio padrão máximo de 0,12C. Os estudos de penetração de calor confirmaram exposições equivalentes a 121C por 24 minutos em todos os itens da carga (F0 > 24 minutos). Em todos os estudos para cargas secas, os índices de capacidade do processo (Cpk) foram maiores que 1,33. Os ensaios de desafio microbiológico garantiram níveis de esterilidade (S.A.L.) maiores que 12 reduções logarítmicas em relação aos indicadores biológicos Geobacillus stearothermophilus. Não foi detectada a presença de endosporos sobreviventes nos 132 indicadores biológicos utilizados nos quatro ciclos desafiados. Com base no planejamento experimental verificou-se que, para o nível de significância de 95% , as mudanças nos fatores posição, embalagem e quantidade da carga não são significativas para o processo de esterilização, em autoclave com remoção forçada de ar. Já para o nível de significância de 90%, a interação Posição x Embalagem apresentou significância estatística no processo de esterilização com valor P de 0,080

A contribution to the knowledge of the skin albuminose cells of Torpedo ocellata Raf [Riv.Istochim.norm.pat. 8 411-416, 1962]

Glandular cells, other than the mucous cells, have been described in the skin of various groups of fish (Teleosts, Ganoids, Selachii) and they have been called 'albuminose' by various authors. The authors propose to study the albuminose cells in the skin of Torpedo ocellata Raf. from a histochemical point of view. The albuminose cells have a complex morphological structure and a correspondingly complicated histochemical make-up. One must treat them as an example of cell with secretions of a particular type, which must and will be better incorporated when more is known of characteristics existent in other species.

Análisis cinemático del robot antropomórfico IRB120 de ABB

[ES]En el siguiente Trabajo Fin de Grado se va a exponer el análisis cinemático y desarrollo de un modelo virtual para la implementación de las ecuaciones cinemáticas del robot IRB120 de ABB llevados a cabo durante el curso 2013/2014. Comenzando por un estudio del Estado del Arte de la robótica industrial, se plantean seguidamente las ecuaciones de localización del robot en función de las variables de entrada mediante el método matricial. Estas ecuaciones son implementadas en un modelo de MatLab para usarlas en la resolución del problema de posición directo e inverso, y son también usadas en herramientas de creación de trayectorias. Además, sus derivadas se utilizan en el cálculo de velocidades del elemento terminal. Por último, se muestra la creación del prototipo 3D del robot, así como un interfaz gráfico de control del robot para el usuario, y los trabajos de validación llevados a cabo de los mencionados modelos virtuales sobre el robot real.