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.

A direct potentiometric titration study of the dissociation of humic acid with selectively blocked functional groups

A direct potentiometric titration method was applied to commercial and soil humic acids in order to determine their carboxyl and phenol group concentrations and apparent and intrinsic pK. In that context, acid-base properties of humic acids are interpreted by selective blocking of carboxylic and phenolic groups by esterification and acetylation. Differences in underivatized and derivatized HA's acid-base properties are ascribed to carboxyl and phenol groups influence on total humic acidity. Potentiometric data were treated with the modified Henderson-Hasselbalch equation. Infra red results, the acidic group contents and the average values of apparent and intrinsic pK for underivatized and derivatized HAs confirmed the selectivity of esterification derivatization method. After blocking of the functional groups, the values of acidic group contents decreased, while the value of apparent pK increased after derivatization. Phenol groups cannot be specifically identified by the acetylation method, due to low selectivity of the acetylation method.

Evaluation of group electronegativities and hardness (softness) of group 14 elements and containing functional groups through density functional theory and correlation with NMR spectra data

Quantum Chemical calculations for group 14 elements of Periodic Table (C, Si, Ge, Sn, Pb) and their functional groups have been carried out using Density Functional Theory (DFT) based reactivity descriptors such as group electronegativities, hardness and softness. DFT calculations were performed for a large series of tetracoordinated Sn compounds of the CH3SnRR'X type, where X is a halogen and R and R' are alkyl, halogenated alkyl, alkoxy, or alkyl thio groups. The results were interpreted in terms of calculated electronegativity and hardness of the SnRR'X groups, applying a methodology previously developed by Geerlings and coworkers (J. Phys. Chem. 1993, 97, 1826). These calculations allowed to see the regularities concerning the influence of the nature of organic groups RR' and inorganic group X on electronegativities and hardness of the SnRR'X groups; in this case, it was found a very good correlation between the electronegativity of the fragment and experimental 119Sn chemical shifts, a property that sensitively reflects the change in the valence electronic structure of molecules. This work was complemented with the study of some compounds of the EX and ER types, where E= C, Si, Ge, Sn and R= CH3, H, which was performed to study the influence that the central atom has on the electronegativity and hardness of molecules, or whether these properties are mainly affected for the type of ligand bound to the central atom. All these calculations were performed using the B3PW91 functional together with the 6-311++G** basis set level for H, C, Si, Ge, F, Cl and Br atoms and the 3-21G for Sn and I atoms.

Potentiometric quantification and speciation of oxygenated groups in humic substances using BEST7 software

In this study the BEST7 software was employed to quantify different classes of functional groups and to model the proton titration behavior of humic substances. To illustrate the process, the Suwannee River fulvic acid of the IHSS (International Humic Substances Society) was used. Five categories - two classes of phenolic groups (phenol and cathecol), two classes of carboxylic groups (benzoic and phtalic) and the combination between them (salicylic) - of oxygenated groups were considered as being responsible for the potentiometric behavior of the sample and were quantitatively determined. The most and the least abundant groups were cathecol (3.300 ± 0.010 mmol g-1) and phenol (1.225 ± 0.070 mmol g-1), respectively. The estimated equilibrium constants were also determined and were in good agreement with the literature values for phenol and cathecol groups and for benzoic, phtalic and salicylic acids. Distribution diagrams of the species were generated with the software SPE and SPEPLOT.

Considering Target Groups in the Creation of a Comprehensive City Branding Process

The aim of the research was to create a comprehensive city branding process. This was done by identifying the key target groups of the city and considering them in the city branding process. Also key stakeholders were identified and taken into consideration when creating the branding process. As an empirical study, three first stages of the city branding process were implemented for the city of Lappeenranta having "students" as the case target group. An interview with the city officials was conducted, as well as a student survey on the current city image of Lappeenranta. Quantitative research methods were used to analyze the results of the survey. A comprehensive city branding process with eight stages was created in the research. Target groups were considered in the process by identifying the target group dependent stages. The empirical study revealed that the current city image held by the students consists of six dimensions. These dimensions were analyzed from the viewpoint of Lappeenranta with the help of an importance performance analysis.

Diameter structure of stratum and ecological groups of a Semideciduous Forest area in Dionísio-MG

The objective of this study was to obtain homogeneous groups of species and information on their density, dominance and volume, in terms of ecological group and diameter structure of an area of Submontane Semideciduous forest (Mata do Mumbaça) in Dionísio, MG. This work was conducted with data of the diameter distribution per species from floristic and phytosociological (Mata do Mumbaça) survey of 120 plots with 10 x 10 m each one. The 120 plots were contiguous and corresponding to a total sample area of 12,000 m² distributed over the topographic units (Low Ramp, Lower Slope, Upper Slope and Hill Top). The topographic units Low Ramp, Lower Slope and Upper Slope were in the middle stage of succession as they presented incipient stratification into two strata (canopy and understory) i.e. canopy ranging from 5 to 12 m high. However, the stratum Hill Top was classified as intermediate/advanced succession because it had a total height equal to or greater than 12 m. The distribution of individual trees of the four strata on diameter classes showed a typical J-inverted pattern that is, high concentration of individuals in smaller diameter classes and a sharp reduction towards the larger classes. In relation to absolute dominance and total volume of species, the ecological group that stood out in the four strata (Low Ramp, Lower Slope, Upper Slope and Hill Top) was the initial secondary, which were in the intermediate stage of secondary, rapidly developing into the mature phase.

Hyvitysmaksujärjestelmä - matka kasettimetristä megatavuun

Pro gradu-tutkielman tarkoituksena on selvittää, millaisia vaikutuksia vaihtoehtoisella yksityisen kopioinnin hyvitysmaksujärjestelmällä voisi olla Suomessa. Hyvitysmaksulla tarkoitetaan korvausta, joka maksetaan oikeudesta tehdä teoskappaleesta kopioita yksityiseen käyttöön. Maksu on Suomessa sisällytetty vuodesta 1984 alkaen kopiointilaitteiden hintoihin ja näin vyörytetty valmistajilta ja maahantuojilta kuluttajien maksettavakasi. Maksun alaisia laitteita ovat esimerkiksi C- kasetit, CD- levyt, digiboxit ja ulkoiset kovalevyt. Tutkielmassa kuvataan hyvitysmaksujärjestelmän historiallista kehitystä nykyiseen muotoonsa, sen toimivuutta eri intressiryhmien näkökulmasta sekä arvioidaan varteenotettavia vaihtoehtoja nykyiselle järjestelmälle. Aina uusiutuvan haasteen hyvitysjärjestelmän kehittämisessä muodostaa teknologian jatkuva muuntuminen ja uusien kopiointitekniikoiden yleistyminen. Siihen tekijänoikeuksia koskevat säädökset ovat vastanneet puutteellisesti tai jälkikäteen. Tutkimuskysymyksiä tarkastellaan virallistenlähteiden, kirjallisuuden ja asiasta julkaistujen, eri intressitahojen kannanottojen perusteella. Tutkimuksen toteutus on sekoitus kvalitatiivista, historiallista ja lainopillista tarkastelua sekä oikeustaloustiedettä. Tutkimuksesta selvisi, että hyvitysmaksujärjestelmä ei tällä hetkellä suoriudu sille asetetuista tehtävistä tyydyttävästi, ja vaihtoehtoisen järjestelmän etsiminen on ajankohtaista. Varteenotettavaksi vaihtoehdoksi yksityiseen käyttöön tapahtuvan kopioinnin korvaamiseksi tekijöille ja tuottajille on tässä tutkielmassa arvioitu korvauksen toteuttaminen viestintärahaston kautta. Tämä ratkaisisi monet nykyiset ongelmat, ja näyttäisi tutkimuksen pohjalta arvioituna olevan paras vaihtoehto. Tähän siirtyminen vaatii kuitenkin ratkaisua kohtuullisen hyvityksen määrittämisen ongelmaan.

Collaborative information behaviour : a case study of two research groups

The aim of the licentiate thesis is to examine researchers' information practices in research groups. The researchers were involved with study communication and media related issues within Social Sciences and Humanities Faculties. The theoretical framework of the study comprises the new holistic models of information seeking (for example: Meho and Tibbo, 2003; Seldén, 1999) and the collective aspects of information behaviour (Prekop, 2002 ; Talja, 2002; Talja and Hansen, 2006). The research questions are: 1. How do scholars seek information in research groups? 2 What kind of collaborative information behaviour occurs in the research groups? The research data was gathered by interviews and observations. Three meetings of a research group at the University of Tampere were observed during the autumn of 2004. The group members and the group leader of the research group were interviewed in the spring of 2005. The research group members and the group leader of a research group at the University of Jyväskylä were interviewed in the autumn of 2005. Altogether, two research group leaders and eight researchers were interviewed. The significance of the research group for information seeking is more important in closeknit research groups than in rather loose research groups. The significance of the research group for information seeking can be at least threefold. First, research group members can inform the group about relevant information resources and potential library or other information services. Second, the research group can to some extent compensate for the information seeking systems of libraries by distributing material and information resources. Third, information seeking can be carried out in collaboration in research groups. The significance of the research group was found to be most important in informing about new information services and marketing library systems. Recommendations from colleagues were often needed to mobilize researchers into using new library services. The significance of colleagues in informing about library services is in line with earlier studies. The present study showed that sometimes information from colleagues was regarded as more important than information distributed directly by the local library. A culture of information sharing, including mutual trust, seemed mainly to be reflected in collaboration and collaborative information seeking in the research groups studied. The timing of the onset of individual research seemed to be related to the information sharing culture and social networks in research groups. The simultaneous onset of the research work by group members seemed to promote the growth of unbiased collaboration, also in information seeking.

Palveluasumisen markkinapotentiaali Suomessa asuvien venäjänkielisten ikäihmisten keskuudessa - Analyysi markkinoista ja kuluttajakäyttäytymisestä

Tutkimus on toimeksianto Yritykseltä X, joka halusi selvitettävän, millaista markkinapotentiaalia on nähtävissä ikäihmisten palveluasumisessa Suomessa asuville venäjänkielisille. Markkinoiden analysoinnin lisäksi tutkimuksessa on selvitetty kohderyhmän kuluttajakäyttäytymistä ja ostokykyä. Tutkimuksen tavoitteena ei ole antaa toimeksiantajalle valmista investointipäätöstä, vaan tuoda tietoa markkinoista ja kohderyhmästä päätöksenteon tueksi. Käytössä on ollut neljä empiiristä aineistoa. Primääriaineistona ovat asiantuntija¬haastattelut sekä kyselyt Yrityksen X venäjänkielisille työntekijöille ja maksaja-asiakkaille – eli kuntien ja sairaanhoitopiirien edustajille. Sekundääriaineistona on joukko suomalaisten Venäjä-asiantuntijoiden viime vuosien tutkimuksia. Pro gradun teoriaosuus on tiivis. Teorian on auttanut kirjoittajaa tarkastelemaan palveluasumisen markkinoita kansainvälisellä vivahteella sekä suomalaisittain uuden kuluttajaryhmän kuluttajakäyttäytymistä ja ostokykyä. Suomessa asuvia venäjänkielisiä ikäihmisiä ei ole aikaisemmassa tutkimuksessa tarkasteltu omana kohderyhmänään, mutta heistä on tehty paljon yhteiskunnallista tutkimusta. Tätä on hyödynnetty muun muassa tarkasteltaessa kohderyhmän kulttuurisia piirteitä, sosiaalisia tapoja, kieltä ja uskontoa. Suomessa asuvista venäjänkielisistä ikäihmistä ei voi puhua yhtenäisenä ryhmänä. Osa yli 65-vuotiaista on suomen kielen taitoisia ja työssään menestyneitä, mutta monen maahanmuuttajan sosiaalinen asema laski heidän muuttaessaan Suomeen. Neuvostoliitossa asuneet ovat tottuneet niukkoihin olosuhteisiin, siihen että samassa taloudessa asui jopa kolme sukupolvea, ja että perhe piti huolta yhteiskunnan tuen ollessa niukkaa. Vaikka venäläisessä kulttuurissa vanhainkodeilla on huono maine, voidaan Suomessa asuvien ikäihmisten keskuudessa nähdä positiivista suhtautumista palveluasumista ja suomalaisia julkispalveluja kohtaan. Mikäli Yritys X rakentaa yksikön Lappeenrantaan, kannattaa potentiaalisina asiakkaina nähdä myös venäläiset terveysmatkailijat ja suunnitella palvelutarjonta laajemmin kuin vain Suomessa asuville venäjänkielisille. Mikäli yksikkö tulee Helsinkiin, on kilpailijana ortodokseille ja venäjänkielisille vanhuksille tarkoitettu Helenan vanhainkoti.

Diarrhea outbreaks in suckling piglets due to rotavirus group C single and mixed (rotavirus groups A and B) infections

Porcine group A rotavirus (PoRVA) is a major cause of neonatal diarrhea in suckling and recently weaned piglets worldwide. The involvement of non-group A rotavirus in cases of neonatal diarrhea in piglets are sporadic. In Brazil there are no reports of the porcine rotavirus group C (PoRVC) as etiologic agent of the diarrhea outbreaks in piglets. The aim of this study was to describe the identification of rotavirus group C in single and in mixed infection with rotavirus groups A and B in three neonatal diarrhea outbreaks in suckling (<21-day-old) piglets, with 70% to 80% and 20% to 25% of morbidity and lethality rates, respectively, in three pig herds located in the state of Santa Catarina, Brazil. The diagnosis of PoRV in the diarrheic fecal samples was performed using polyacrylamide gel electrophoresis (PAGE) to identify the presence of porcine rotavirus groups A, B (PoRVB), and C, and by RT-PCR (PoRVA and PoRVC) and semi-nested (SN)-PCR (PoRVB) to partially amplify the VP4 (VP8*)-VP7, NSP2, and VP6 genes of PoRVA, PoRVB, and PoRVC, respectively. One RT-PCR (PoRVA and PoRVC) and SN-PCR (PoRVB) product of each group of rotavirus of each diarrhea outbreak was submitted to nucleotide (nt) sequence analysis. Based on the PAGE technique, 4 (25%) and 1 (6.25%) of the 16 diarrheic fecal samples evaluated in the first outbreak presented PoRVA and PoRVC electropherotype, respectively, and 11 (68.75%) were negative. In the second outbreak, 3 (42.85%) of the 7 fecal samples evaluated presented PoRVA electropherotype, and in 3 (42.85%) and in 1 (14.3%) fecal samples were detected inconclusive and negative results, respectively. Three (30%) of the 10 fecal samples of the third outbreak presented PoRVC electropherotype; 5 (50%) and 2 (20%) samples showed negative and inconclusive results, respectively. Based on the RT-PCR and SN-PCR assays in the first neonatal diarrhea outbreak, PoRVC was detected in 13 (81.2%) of the 16 diarrheic fecal samples evaluated. PoRVC single infection was identified in 4 (25%) of these samples and mixed infections with PoRVA and PoRVB in 9 (56.2%) fecal samples. All of the seven diarrheic fecal samples evaluated from the second neonatal diarrhea outbreak were positive for PoRVC, whereas its mixed infection with other PoRV groups was detected in 4 (57.2%) samples. In the third outbreak, PoRVC in single infection was detected in all of the 10 diarrheic fecal samples analyzed. In the nt sequence analysis, the PoRVA strains of the first and second outbreaks demonstrated higher nt identity with G4P[6] and G9P[23] genotypes, respectively. The PoRVB strains (first and second outbreaks) and the PoRVC strains (first, second, and third outbreaks) showed higher nt identity and clustered in the phylogenetic tree with PoRVB and PoRVC strains that belong to the N4 and I1 genotypes, respectively. This is the first description in Brazil of the involvement of PoRVC in the etiology of diarrhea outbreaks in suckling piglets. The results of this study demonstrated that PoRVC, in both single and mixed infections, is an important enteropathogen involved in neonatal diarrhea outbreaks in piglets and that the use of more sensitive diagnostic techniques allows the identification of mixed infections involving two or even three groups of PoRV, which may be more common than previously reported.

Network connectance and autonomy analyses of the photosynthetic apparatus in tropical tree species from different successional groups under contrasting irradiance conditions

Biological systems are complex dynamical systems whose relationships with environment have strong implications on their regulation and survival. From the interactions between plant and environment can emerge a quite complex network of plant responses rarely observed through classical analytical approaches. The objective of this current study was to test the hypothesis that photosynthetic responses of different tree species to increasing irradiance are related to changes in network connectances of gas exchange and photochemical apparatus, and alterations in plant autonomy in relation to the environment. The heat dissipative capacity through daily changes in leaf temperature was also evaluated. It indicated that the early successional species (Citharexylum myrianthum Cham. and Rhamnidium elaeocarpum Reiss.) were more efficient as dissipative structures than the late successional one (Cariniana legalis (Mart.) Kuntze), suggesting that the parameter deltaT (T ºCair - T ºCleaf) could be a simple tool in order to help the classification of successional classes of tropical trees. Our results indicated a pattern of network responses and autonomy changes under high irradiance. Considering the maintenance of daily CO2 assimilation, the tolerant species (C. myrianthum and R. elaeocarpum) to high irradiance trended to maintain stable the level of gas exchange network connectance and to increase the autonomy in relation to the environment. On the other hand, the late successional species (C. legalis) trended to lose autonomy, decreasing the network connectance of gas exchange. All species showed lower autonomy and higher network connectance of the photochemical apparatus under high irradiance.

Photosynthetic responses of tropical tree species from different successional groups under contrasting irradiance conditions

This study evaluated the photosynthetic responses of seven tropical trees of different successional groups under contrasting irradiance conditions, taking into account changes in gas exchange and chlorophyll a fluorescence. Although early successional species have shown higher values of CO2 assimilation (A) and transpiration (E), there was not a defined pattern of the daily gas exchange responses to high irradiance (FSL) among evaluated species. Cariniana legalis (Mart.) Kuntze (late secondary) and Astronium graveolens Jacq. (early secondary) exhibited larger reductions in daily-integrated CO2 assimilation (DIA) when transferred from medium light (ML) to FSL. On the other hand, the pioneer species Guazuma ulmifolia Lam. had significant DIA increase when exposed to FSL. The pioneers Croton spp. trended to show a DIA decrease around 19%, while Cytharexyllum myrianthum Cham. (pioneer) and Rhamnidium elaeocarpum Reiss. (early secondary) trended to increase DIA when transferred to FSL. Under this condition, all species showed dynamic photoinhibition, except for C. legalis that presented chronic photoinhibition of photosynthesis. Considering daily photosynthetic processes, our results supported the hypothesis of more flexible responses of early successional species (pioneer and early secondary species). The principal component analysis indicated that the photochemical parameters effective quantum efficiency of photosystem II and apparent electron transport rate were more suitable to separate the successional groups under ML condition, whereas A and E play a major role to this task under FSL condition.

Ecological distribution of stream macroalgae in different spatial scales using taxonomic and morphological groups

We examined the ecological distribution of macroalgal communities in streams using species groups (taxonomic units = algal phyla, and morphological = morphological types) with similar structures and functions instead of the species themselves. The study was conducted from June to July/2007 in two drainage basins located in mid-southern region of Paraná State , Brazil. Evaluations of macroalgal communities took into consideration the following spatial scales: the drainage basin (the Pedras river and Marrecas river basins), shading regime (open and shaded stream segments), mesohabitats (riffles and pools), and microhabitats (sampling units of 0.05m2). A total of 29 taxa (23 subgeneric, one generic, and five vegetative groups) were identified. On these, 12 taxa belong to Chlorophyta, 11 to Cyanobacteria, four to Heterokontophyta, and two to Rhodophyta. The proportions of morphological types were: 24% free filaments, 17.25% mats, tufts, gelatinous colonies, and gelatinous filaments, 7% crusts. In terms of spatial scales, we observed a predominance of Chlorophyta in open stream segments and Cyanobacteria in shaded stream segments, reflecting the loss of competitive advantage of green algae in sites with low energy availability. In the mesohabitats, the morphological types recorded in pools were predominantly poorly adapted to fast currents (free filaments), while those found in riffles (mats, tufts and gelatinous filaments) were highly resistant to fast water flows. As such, the use of species groupings based on algal taxonomy associated with morphological characteristics proved to be useful to understanding the distributions of these organisms in lotic environments.