p-Nitrobenzyloxycarbonyl (pNZ) as Temporary Na-Protecting Group for Mild Solid-Phase Peptide Synthesis. Avoiding Diketopiperazine and Aspartimide Formation

p-Nitrobenzyloxycarbonyl was used as temporary protecting group for the -amino function in solid-phase peptide synthesis. The corresponding derivatives are solids, easy to be synthesized, and perform well in the solid-phase mode. pNZ is removed in practical neutral conditions in the presence of catalytic amounts of acid. They are orthogonal with the most common protecting groups used in peptide chemistry. They are specially useful in combination with Fmoc chemistry to overcome those side reactions associated with the used of the piperidine such DKP and aspartiimide formation. The flexibility of pNZ can be very useful for the preparation of libraries of small organic molecules.

World Polarization in carbon emissions, potential conflict and groups: an updated revision

Typically, conflicts in world environmental negotiations are related, amongst other aspects, to the level of polarization of the countries in groups with conflicting interests. Given the predictable relationship between polarization and conflict, it would seem logical to evaluate the degree to which the distribution of countries – for example, in terms of their CO2 emissions per capita – would be structured through groups which in themselves are antagonistic, as well as their evolution over time. This paper takes the concept of polarization to explore this distribution for the period 1992-2010, looking at different analytic approaches related to the concept. Specifically, it makes a comparative evaluation of the results associated with endogenous multi-polarization measures (i.e. EGR and DER indices), exogenous measures (i.e. Z-K or multidimensional index) and strict bipolarization measures (i.e. Wolfson’s measure). Indeed, the interest lies not only in evaluating the global situation of polarization by comparing the different approaches and their temporal patterns, but also in examining the explanatory capacity of the different proxy groups used as a possible reference for designing global environmental policy from a group premise. JEL codes: D39; Q43; Q56. Key words: polarization; carbon emissions; conflict;

Brief report : Academic amotivation in light of the dark side of identity formation

The study intended to determine motivational profiles of first-year undergraduates and aimed their characterization in terms of identity processes. First, a cluster analysis revealed five motivational profiles: combined (i.e., high quantity of motivation, low amotivation); intrinsic (i.e., high intrinsic, low introjected and external regulation, low amotivation); "demotivated" (i.e., very low quantity of motivation and amotivation); extrinsic (i.e., high extrinsic and identified regulation and low intrinsic and amotivation); and "amotivated" (i.e., low intrinsic and identified, very high amotivation). Second, using Lebart's (2000) methodology, the most characteristic identity processes were listed for each motivational cluster. Demotivated and amotivated profiles were refined in terms of adaptive and maladaptive forms of exploration. Notably, exploration in breadth and in depth were underrepresented in demotivated students compared to the total sample; commitment and ruminative exploration were under and overrepresented respectively in amotivated students. Educational and clinical implications are proposedand future research is suggested.

Versatile methodology to hydrate alkynes, in the presence of a wide variety of functional groups, with Mercury(II) p-Toluensulfonamidate, under catalytic, mild and neutral conditions

A method to generate carbonylic compounds from alkynes under mild and neutral conditions, with excellent functional group compatibility and high yields, is described. Hydration takes place under catalytic conditions by using from 0.1 to 0.2 equivalents of the easily available and inexpensive mercury(II) p-toluensulfonamidate in a hydroalcoholic solution. After use the catalyst is iner tized and/or recycled ...

Estudos de QSAR baseados em dados de atividade biológica obtidos por microcalorimetria: III interação de m-alcoxifenóis e p-hidroxibenzoatos de alquila com Escherichia coli

QSAR studies based on flow microcalorimetric bioassay data for interaction of homologous series of m-alkoxyphenols and p-hydroxybenzoates with E. coli cells were carried out applying factorial design. Results for both series showed a linear relationship between log(dose)max and log Po/w. Analysis of these data allows the identification of contributions toward the derived bioactivity from the parent structures (the molecule minus n-CH2 groups present in the side-chain) and the lipophilic groups, CH2. These results are discussed with respect to drug quantitative structure-relationship.

Alcatrão ou creosoto de eucalipto na produção de adesivos fenólicos para colagem de madeira

This study has shown that Eucalyptus tar and creosote can be used in phenolic adhesive formulations (resols) for wood products bonding. Some adhesives were prepared substituting 0; 17.7; 35.0 and 67.0% of the phenol by anhydrous tar and 0; 15.0 e 28.5% by creosote. In gluing Brazilian pine veneers, eucalypt tar and creosote based adhesives required longer pressing times for curing than conventional phenol-formaldehyde adhesives. By using 13C NMR, the number of carbons in side chains and hydroxyl, carbonyl, carboxyl and methoxyl groups related to 100 aromatic rings could be estimated in tar and creosote. In creosote, after reaction with excess formaldehyde in alkaline medium, only 0,28 hydroxymethyl groups was detected per phenolic ring. This low amount of hydroxymethylation explains the lack of reactivity in curing observed when creosote was introduced in a standard adhesive formulation.

Computing the diameter of Coxeter groups

This thesis addresses the problem of computing the minimal and maximal diameter of the Cayley graph of Coxeter groups. We first present and assert relevant parts of polytope theory and related Coxeter theory. After this, a method of contracting the orthogonal projections of a polytope from Rd onto R2 and R3, d ¸ 3 is presented. This method is the Equality Set Projection algorithm that requires a constant number of linearprogramming problems per facet of the projection in the absence of degeneracy. The ESP algorithm allows us to compute also projected geometric diameters of high-dimensional polytopes. A representation set of projected polytopes is presented to illustrate the methods adopted in this thesis.

Convergent Approaches for the Synthesis of the Anti-tumoral Peptide, Kahalalide F. Study of Orthogonal Protecting Groups

Kahalalide compounds are peptides that are isolated from a Hawaiian herbivorous marine species of mollusc, Elysia rufescens, and its diet, the green alga Bryopsis sp. Kahalalide F and its synthetic analogues are the most promising compounds of the Kahalalide family because they show anti-tumoral activity. Linear solid-phase syntheses of Kahalalide F have been reported. Here we describe several new improved synthetic routes based on convergent approaches with distinct orthogonal protection schemes for the preparation of Kahaladide analogues. These strategies allow a better control and characterization of the intermediates because more reactions are performed in solution. Five derivatives of Kahalalide F were synthesized using several convergent approaches.

Treatment-related renal side-effects in pediatric cancer patients

Background: The long-term side-effects of cancer treatments are of growing importance, since the number of pediatric cancer survivors has considerably increased. Renal side-effects should be noted early to prevent further deterioration. Renal dysfunction may also develop long after cancer treatment. Easy and reliable methods for assessing renal function are needed. Aims: The aims were to find the mechanisms behind methotrexate-induced renal damage by studying renal tubular cells (LLC-PK1cells), and to evaluate the usefulness of laboratory tests in assessing glomerular function in pediatric cancer patients by comparing an isotope clearance method with alternative methods. The aim was also to study the long-term effects of bone marrow transplantation (BMT) and high-dose methotrexate (HD-MTX) treatment in renal function. Results: Methotrexate induced time-dependent renal tubular cell swelling and cell death. In patients treated with HD-MTX a significant decrease in GFR was noted after a follow-up time of one to ten years. One year after BMTthe GFR was reduced, especially in patients treated with total body irradiation (TBI). GFR recovered slightly but remained stable thereafter. In glomerular function assessment the serum cystatin C (cysC) concentration showed a significant association with GFR measured by the isotope method. Conclusions: Methotrexate induced acute damage in renal tubular cells. In assessing GFR the isotope method still remains the method of choice, but the assay of cystatin C was the most reliable of other alternatives. Long-term follow-up of renal function is needed in BMT patients and patients treated with HD-MTX.

Strategic groups and performance: an empirical analysis of strategic groups in the wind energy industry in Europe

The strategic group theory provides an intermediate level of analysis between a single company and the whole industry for identifying issues about the company's competitive position and strategic choices. Strategic groups are companies within an industry with similar strategic characteristics or competing on similar bases. Strategic choices are aligned with the firms’ resources. The purpose of this study was to identify the strategic groups in the wind energy industry in Europe, and study, whether a certain group membership results in financial performance differences. Altogether 80 European wind energy companies were included in the study, which were clustered into four strategic groups according to their age and growth rate. Each group corresponds to a different strategy. The results show that the wind energy companies can be clustered according to the chosen strategic characteristics. Strategic decisions were investigated with characteristic variables. Performance variables were used in the analysis measuring profitability, liquidity and solvency of the groups. These strategic choices of the companies did not have a significant influence on the firms’ performance. The more mature and slower growing group proved to be the most successful. However, the differences between groups were generally not statistically significant. The only statistically significant difference found was in the solvency ratio between Mature Slow and Young Rapid groups. Measured with these variables, more mature and slower growing companies performed better. Therefore, a certain strategic group membership results in performance differences.

Essential factors for control of the equilibrium in the reversible rearrangement of M3N@Ih-C80 fulleropyrrolidines: Exohedral functional groups versus endohedral metal clusters

The effects of exohedral moieties and endohedral metal clusters on the isomerization of M3N@Ih-C80 products from the Prato reaction through [1,5]-sigmatropic rearrangement were systematically investigated by using three types of fulleropyrrolidine derivatives and four different endohedral metal clusters. As a result, all types of derivatives provided the same ratios of the isomers for a given trimetallic nitride template (TNT) as the thermodynamic products, thus indicating that the size of the endohedral metal clusters inside C80 was the single essential factor in determining the equilibrium between the [6,6]-isomer (kinetic product) and the [5,6]-isomer. In all the derivatives, the [6,6]- and [5,6]-Prato adducts with larger metal clusters, such as Y3N and Gd3N, were equally stable, which is in good agreement with DFT calculations. The reaction rate of the rearrangement was dependent on both the substituent of exohedral functional groups and the endohedral metal-cluster size. Further DFT calculations and 13C NMR spectroscopic studies were employed to rationalize the equilibrium in the rearrangement between the [6,6]- and [5,6]-fulleropyrrolidines

The adequacy of different robust statistical tests in comparing two independent groups

In the current study, we evaluated various robust statistical methods for comparing two independent groups. Two scenarios for simulation were generated: one of equality and another of population mean differences. In each of the scenarios, 33 experimental conditions were used as a function of sample size, standard deviation and asymmetry. For each condition, 5000 replications per group were generated. The results obtained by this study show an adequate type error I rate but not a high power for the confidence intervals. In general, for the two scenarios studied (mean population differences and not mean population differences) in the different conditions analysed, the Mann-Whitney U-test demonstrated strong performance, and a little worse the t-test of Yuen-Welch.

Menestyksekkäät yliopistopelin pelaajat? Tutkimus nopeasti ja nuorena valmistumisesta

Succestul players of the university game? A study about the short duration of master’s degree studies and graduating at a young age The duration of studies has long been a topic of conversation. It was first mentioned in 1883, but the discussion has been quite active and topical for the last fifty years. During that time, there have been numerous committees, working groups for the Ministry of Education, and revisions to the structure of the master’s degree program. All of these have focused on lowering the duration of studies as well as the age at which students graduate. These two factors have been regarded as indicators of efficiency. Achieving these goals is seen to promote the successful transition from studies to work. In addition, the greater time that people spend working is thought to help with the fiscal burden of an aging population. The reasons for prolonged study seem to be: students working during the course of their studies; the actual workload of the studies, which sometimes does not correlate with the calculated workload; problems with the students’ course selections and with their financial support from the government; issues in teaching; and problems with university funding. This study focuses on students’ study experiences, their progress, and the university itself. Of particular interest was the students’ use of different resources—cultural, social, and economical capital. Participants in the study had graduated from the University of Turku between the years of 1999 and 2001 and were divided into two groups: prompt graduates, those who graduated among the fastest 18th percent in their faculty; and those who graduated at a slower pace. A survey (N=499) and interviews (N=69) were among the methods used, along with a compilation of statistics on the students’ duration of studies, the number of modules studied, and marks obtained. Bourdieu’s theory about fields and the games people play in those fields formed the theoretical background of this study. The university was seen to form a playing field with historically and politically changeable rules. The students playing in this field were considered to possess different economical, social, and cultural resources, which they use more or less successfully. Some of the strategies used by students result in gra¬duating at a young age and/or a short duration of study; some do not. This study divided the age of graduation and the duration of study into separate games. This allowed the study to determine the relationship between these two factors and to examine their similarities and differences. The study also focused on the idea of success. Short duration of studies and a young graduation age can be considered, be some, an indication of success in navigating the university field. This study aimed to see if this concept held true or whether these seeming indicators of success have negative side effects. The main result of this study is that, even though the games of duration and age have similarities, they are sufficiently diverse to be considered separate games, which need different resources. To graduate with a short duration of studies, it is important for a student to successfully view and navigate the university field, tailoring one’s studies and extracurricular activities to suit the individual. In the game of youth, the background of the student seemed to be of greater importance. The youngest graduates had spent more time with their parents, who also had higher educational qualifications. They also had higher achievement in their previous studies. This seems to indicate that their background allowed them to assimilate a better understanding of the school and university fields and that playing the university game was natural for them. As for the aspect of success, it seems that there are many ways to define the term. Youth on graduation and short duration of studies can be seen as two indicators of success. Both revealed negative and positive outcomes, even though short duration of studies seemed more often to be connected with positive outcomes. However, it seems that the best indicator for success is the way in which students organize study into their lives to support and suit their needs and abilities to realize a meaningful life and a successful entry into the field of work.

Realització d'una aplicació de gestió de xarxes per a la xarxa sensefils de Manresa GuifiBages

En els últims anys, la popularitat de les xarxes sensefils (WIFI) ha anat en augment a un ritme incansable. Des de petits aparells instal•lats a les cases amb aquesta tecnologia com a complement dels routers d’accés a internet instal•lats per diverses companyies, fins a empreses fent petits desplegaments per comunicar entre si les seves seus. Al marge d’aquests escenaris, s’ha produït un fenomen social d’acolliment d’aquesta tecnologia a nivell mundial, en forma del que coneixem com a xarxes ciutadanes / xarxes lliures / xarxes socials. Aquestes xarxes han estat possibles gràcies a diverses raons que han fet assequible a col•lectius de persones, tant els aparells com els coneixements necessaris per dur a terme aquestes actuacions. Dintre d’aquest marc, al Bages, concretament a Manresa, es va començar a desenvolupar una d’aquestes xarxes. Les decisions d’aquesta xarxa d’utilitzar exclusivament hardware i software de codi obert, i determinats aspectes tècnics de la xarxa, ha comportat que la xarxa fos incompatible amb algunes de les aplicacions de gestió de xarxes existents desenvolupades per comunicats com gufi.net a Osona. És per això que per garantir el creixement, la supervivència i l’èxit d’aquesta xarxa en el temps, és indispensable poder comptar amb una eina de gestió que s’adigui a les característiques de GuifiBages. L’objectiu principal d’aquest treball és dotar a la xarxa GuifiBages de les eines necessàries per poder gestionar tota la informació referent a l’estructura de la seva xarxa, tant per facilitar l’accés a nous usuaris sense molts coneixements tècnics, com per facilitar nous desplegaments / reparacions / modificacions de la xarxa d’una manera automàtica. Com a conclusió d’aquest treball, podem afirmar que les avantatges que proporciones tecnologies com Plone, faciliten enormement la creació d’aplicacions de gestió de continguts en entorn web. Alhora, l’ús de noves tècniques de programació com AJAX o recursos com els que ofereix Google, permeten desenvolupar aplicacions web que no tenen res a envejar al software tradicional. D’altra banda, voldríem destacar l’ús exclusiu de programari lliure tant en els paquets de software necessaris pel desenvolupament, com en el sistema operatiu i programes dels ordinadors on s’ha dut a terme, demostrant que es poden desenvolupar sistemes de qualitat sense dependre de programari privatiu.

Prognostic Markers and Prolonged Interferon-alpha Therapy in Renal Cell Carcinoma

Molekyylimarkkerit ja pitkäaikainen alfainterferonihoito munuaissyövässä Munuaissyöpäpotilaiden viiden vuoden elossaololuku on noin 50 %. Aikaisempien tutkimuksien mukaan viiden vuoden elossaololuku metastasoituneessa munuaissyövässä on 3-16 %, kun käytettiin alfainterferonia sisältävää hoitoa. Tyypillisesti alfainterferonia on käytetty vähemmäin kuin 6 kuukautta. Avoimia kysymyksiä ovat alfainterferonin optimaalinen hoitoannos ja hoidon kesto yksin tai yhdessä uusien täsmähoitojen kanssa. Tärkeimmät tavoitteet olivat tutkia 1) jaksotetun pitkäaikaisen alfainterferonihoidon tehoa ja siedettävyyttä metastasoituneessa munuaissyövässä ja 2) p53-, Ki-67- ja COX-2-proteiinituotannon ennusteellista merkitystä munuaissyövässä. Tutkimuksessa 117 metastasoituneelle munuaissyöpää sairastaneelle potilaalle etsittiin yksilöllinen hänen sietämänsä maksimaalinen hoitoannos rekombinanttia alfa2a-interferonia (Roferon-ATM). Hoitoa pyrittiin jatkamaan 24 kuukauden ajan. Kolmen hoitoviikon jälkeen pidettiin yhden viikon tauko. Hoito lopetettiin, jos ilmaantui vakavia haittavaikutuksia tai tauti eteni. Toisessa tutkimuksessa proteiinituotanto analysoitiin immunohistokemiallisesti munuaissyöpäpotilaiden kasvainnäytteistä, joita oli säilytetty parafiinissa. Kasvainnäytteet oli otettu talteen munuaisen poistoleikkauksen yhteydessä. Nämä potilaat jaettiin kolmeen eri ryhmään: metastasointi primaarivaiheessa (n=29), metastasointi myöhemmin (n=37) ja ei metastasointia (n=51). Keskimääräinen alfainterferonihoidon kesto oli 11 kuukautta (kk) [0,5 – 32 kk]. Objektiivinen hoitovaste todettiin 17 %:lla, tautitilanne pysyi ennallaan 42 %:lla ja myöhäinen vaste (yli 12 kk:tta hoidon aloittamisesta) todettiin 3 %:lla. Aika vasteen saavuttamisesta taudin etenemiseen oli keskimäärin 8 kk ja elinaika 19,1 kk. Viiden vuoden elossaololuku oli 16 %. Jos metastasoituneella munuaissyöpäpotilaalla oli keuhkometastasointi, hän selvisi todennäköisemmin viisi vuotta kuin muut potilaat. Henkeä uhkaavia sivuvaikutuksia ei todettu. Yli 12 kk:n ajan kestävä alfainterferonihoito on hyödyllistä niille potilaille, jotka ovat saaneet objektiivisen hoitovasteen tai tautitilanne on pysynyt ennallaan. Positiivinen p53- ja Ki-67-ekspressio yhdessä viittaavat suureen metastasoinnin todennäköisyyteen. Positiivinen COX-2-ekspressio viittaa viivästyneeseen metastaasien ilmaantumiseen. Metastasoituneilla potilailla positiiviset p53- ja Ki-67-ekspressiot viittaavat huonoon ennusteeseen, mutta positiivinen COX-2 ekspressio viittaa suotuisaan ennusteeseen. Positiivinen COX-2- ja negatiivinen Ki-67-ekspressio yhdessä viittaavat parantuneeseen ennusteeseen metastasoituneessa munuaissyövässä.