13c And 1h Nmr Study Of Complexes Of 2-Pyridinethione And 4-Pyridinethione With Zn(Ii), Cd(Ii) And Hg(Ii) Halides

Proton and carbon-13 NMR has been used to study complexes of 2-pyridinethione (in its basic and deprotonated forms) and 4-pyridinethione with zinc(II), cadmium(II) and mercury(II) halides. The variations in the carbon-13 and proton chemical shifts are discussed.

Structural Analysis by X-Ray Diffraction of a Polar Mesogen 4-Cyanobiphenyl-4'-heptylbiphenyl Carboxylate

Crystal and molecular structure of a compound 4-cyanobiphenyl-4'-heptylbiphenyl carboxylate (7CBB), which exhibit both monolayer smectic A and nematic phases, have been determined by direct methods using single crystal X-ray diffraction data. The structure is monoclinic with the space group P21/c and Z = 4. The unit cell parameters are a = 16.9550(5) Aring, b = 5.5912(18) Aring, c = 27.5390(9) Aring, agr = 90.000°, β = 93.986(6)°, and γ = 90.000°. Packing of the molecules is found to be precursor to SmC phase, although SmA1 phase is observed on melting. Several strong van der Waals interactions are observed in the core part of the neighboring molecular pairs. Crystal to mesophase transition is probably of reconstitutive nature. Geometry, packing, and nature of crystal-mesophase transition are compared to those in 6CBB.

1-(2,4-Dichlorophenyl)-3-[4-(dimethylamino)-phenyl]prop-2-enone

In the title compound, C17H15Cl2NO, the dimethylaminophenyl group is close to coplanar with the central propenone group [dihedral angle =13.1 (1)degrees between the mean planes], while the dichlorophenyl group is twisted from the plane [dihedral angle = 64.0 (1)degrees].In the crystal, C-H center dot center dot center dot O and weak C-H center dot center dot center dot pi interactions are formed between molecules.

4-(4-Methoxyphenyl)-1-phenylpyridine-2,6(1H,3H)-dione

In the title compound, C18H15NO3, the pyridine-2,6-dione ring adopts an envelope conformation. The phenyl ring lies approximately perpendicular to the mean plane of the pyridine-2,6-dione ring [dihedral angle =81.5 (1)degrees], while the methoxyphenyl ring is tilted to the same plane by a dihedral angle of 34.8 (1)degrees. Intermolecular C-H center dot center dot center dot O interactions link the molecules into chains along [100].

4-[2-(1-Acetyl-2-oxopropylidene)-hydrazino]-N-(pyrimidin-2-yl)benzenesulfonamide

In the title compound, C15H15N5O4S, the dihedral angle between the pyrimidine and benzene rings is 84.56 (2)degrees. Intramolecular hydrazine-carbonyl N-H center dot center dot center dot O and intermolecular sulfonamide-pyridimine N-H center dot center dot center dot N hydrogen bonds stabilize the molecular and crystal structures, respectively.

Sekä että : Ironia koherenssina ja inkoherenssina

The interpretation of irony in this study is seen as being crucially dependent on the notion of coherence. Coherence depends on a complex interplay of contextual features, which is why all interpretations must be seen as socio-cultural processes. An utterance is perceived as coherent if it makes sense and if it hangs together. Incoherent utterances can result in an ironic interpretation; however, the incoherence must also be perceived as being intentional, and intentionality in turn is a sign of the ironist's rejecting stance. The study does not encompass the notion of irony of fate nor situational irony that is unintentional. Irony is defined in this study as a combination of five components. It is seen as (1) a negative attitude that reflects (2) the intention of the ironist, and (3) has a target and most often (4) a victim too. Essential to irony is its fifth component, the fact that one or more of these four components must be inferred from co- or context. The componential definition of irony is crucial in deciding whether an interpretation is ironic or not, and the definition makes it possible to discern the differences as well as the similarities between different kinds of irony. The method of the study is experimental: 12 Finnish newspaper texts that could be considered to be ironic were interpreted by 107 informants. The interpretation of one of the texts was based on unelicited feedback given by readers of a weekly magazine. The responses were analyzed to determine (a) whether the texts were perceived as being coherent or incoherent and (b) whether the informants appealed to any of the five components of irony. The results of the analyses of the informants' responses indicate that differences between the ironic and non-ironic interpretations of the texts can be explained in terms of whether or not the informant regarded the text as being coherent. The thesis also discusses the shortcomings of other accounts of irony: the Gricean theory of conversational implicature, speech act theory, irony as rhetoric, irony as pretense, irony as echoic mention, and irony as framing. In contrast to these other accounts, the study focuses on irony as a textual phenomenon and underlines the importance of socio-cultural context in the interpretation of irony. Key words: irony, coherence, incoherence, the componential definition of irony, interpretation of linguistic utterances.

An infrared spectroscopic study of the incommensurate transitions and related phase changes in K2Pb[Cu(NO2)6] and [N(CH3)4]2MX4 (M = Mn, Co, Cu or Zn and X = Cl or Br)

K2Pb[Cu(NO2)6] and [N(CH3)4]2MX4 (M = Mn, Co, Cu or Zn and X = Cl or Br) undergo phase transitions which involve incommensurate phases. The transitions have been investigated by examining the changes in the NO2 and CH3 vibration bands in the i.r. spectra. Splitting and broadening of some of the bands across the incommensurate transitions are discussed in the context of geometrical restrictions in the incommensurate phases. The phase transitions have also been characterized using differential scanning calorimetry.

5,7-Dimethoxy-2-phenyl-4H-chromen-4-one

The asymmetric unit of the title compound, C17H14O4, contains two independent molecules which differ in the relative orientations of the phenyl rings with repect to the essentially planar [maximum deviations of 0.029 (2) and 0.050 (2) angstrom in the two molecules] chromene fused-ring system, forming dihedral angles of 10.3 (5) and 30.86 (5)degrees in the two molecules. The crystal structure is stabilized by weak C-H center dot center dot center dot O and C-H center dot center dot center dot pi interactions, and pi-pi stacking interactions.

Characterization of disease resistance gene candidates of the nucleotide binding site (NBS) type from banana and correlation of a transcriptional polymorphism with resistance to Fusarium oxysporum f.sp. cubense race 4

Most plant disease resistance (R) genes encode proteins with a nucleotide binding site and leucine-rich repeat structure (NBS-LRR). In this study, degenerate primers were used to amplify genomic NBS-type sequences from wild banana (Musa acuminata ssp. malaccensis) plants resistant to the fungal pathogen Fusarium oxysporum formae specialis (f. sp.) cubense (FOC) race 4. Five different classes of NBS-type sequences were identified and designated as resistance gene candidates (RGCs). The deduced amino acid sequences of the RGCs revealed the presence of motifs characteristic of the majority of known plant NBS-LRR resistance genes. Structural and phylogenetic analyses grouped the banana RGCs within the non-TIR (homology to Toll/interleukin-1 receptors) subclass of NBS sequences. Southern hybridization showed that each banana RGC is present in low copy number. The expression of the RGCs was assessed by RT-PCR in leaf and root tissues of plants resistant or susceptible to FOC race 4. RGC1, 3 and 5 showed a constitutive expression profile in both resistant and susceptible plants whereas no expression was detected for RGC4. Interestingly, RGC2 expression was found to be associated only to FOC race 4 resistant lines. This finding could assist in the identification of a FOC race 4 resistance gene.

Paavo Ravila ja Leonard Bloomfield kielitieteen oppihistoriassa : Vertaileva tutkimus tutkijankuvasta ja tieteenfilosofiasta

Tämä tutkielma käsittelee Paavo Ravilan (1902–1974) ja Leonard Bloomfieldin (1887–1949) tieteenfilosofisia näkemyksiä ja heistä muodostunutta tutkijankuvaa. Työn näkökulma on oppihistoriallinen, ja sen tavoitteena on selvittää Ravilan ja Bloomfieldin teoreettisten näkemysten yhtäläisyyksiä. Työn pääasiallinen lähdekirjallisuus sisältää sekä kotimaista että kansainvälistä kielitieteen historiankirjoitusta. Aineistona on Ravilan ja Bloomfieldin teoreettisen tason kirjoitukset kielitieteestä ja tieteenfilosofiasta; näin ollen heidän kielitieteelliset tutkimuksensa jäävät työn ulkopuolelle. Työtä varten on käytetty myös arkistolähteitä sekä ulkomailta että Suomesta. Ravilan kansainvälisyyttä käsiteltäessä arvokasta aineistoa ovat varsinkin yhdysvaltalaisten yliopistojen arkistoista löytynyt kirjeenvaihto ja muu arkistomateriaali. Luvussa 2 esitellään yleistä kielitieteen historiaa 1800-luvulta 1960-luvulle. Luvussa 3 käsitellään Ravilan ja Bloomfieldin elämää ja uraa ja analysoidaan heistä muodostunutta tutkijankuvaa. Luvussa 4 käsitellään niitä tieteenfilosofisia kysymyksiä, joissa Ravilan ja Bloomfieldin ajatusten samankaltaisuus parhaiten tulee esille: empirismiä, positivismia, merkitystä, formalismia sekä synkronian ja diakronian suhdetta. Ravila ja Bloomfield painottivat empiristisen asennoitumisen tärkeyttä kielitieteessä erityisesti suhteessa aineistoon ja siitä tehtäviin päätelmiin. Lisäksi molemmat olivat positivisteja ja vastustivat siksi sellaisia selityksiä, joita ei voi perustella aineistosta käsin suorien havaintojen avulla. Myös molemmilla toistuva tieteellisyyden vaatimus on johdettavissa positivistisesta asennoitumisesta. Kielitieteen oppihistoriassa Ravilan ja Bloomfieldin tutkijankuva on erilainen varsinkin suhteessa merkityksentutkimukseen, mutta heidän kannanottojensa yksityiskohtaisempi tarkastelu osoittaa, että heidän näkemyksistään voidaan löytää yllättäviä samankaltaisuuksia. Myös synkronian ja diakronian suhdetta tutkittaessa voidaan havaita yhtymäkohtia: synkronistina pidetty Bloomfield ja diakronistina pidetty Ravila pitivät molemmat parhaana lähestymistapana kieleen synkronian ja diakronian yhdistävää tutkimusotetta. Vertailemalla Ravilan ja Bloomfieldin tieteenfilosofisia näkemyksiä voidaan havaita, että heidän käsityksensä kielitieteestä on monilta osin yhteneväinen. Lisäksi vertailu avaa mielenkiintoisia näkökulmia Ravilan suhteeseen suomalaiseen kielitieteeseen. Esimerkiksi positivismin mukainen metafysiikkavastaisuus erottaa hänet ajan eurooppalaisesta kielitieteestä ja toisaalta yhdistää häntä yhdysvaltalaiseen kielitieteeseen.

Pitch discrimination in optimal and suboptimal acoustic environments: electroencephalographic, magnetoencephalographic, and behavioral evidence

Pitch discrimination is a fundamental property of the human auditory system. Our understanding of pitch-discrimination mechanisms is important from both theoretical and clinical perspectives. The discrimination of spectrally complex sounds is crucial in the processing of music and speech. Current methods of cognitive neuroscience can track the brain processes underlying sound processing either with precise temporal (EEG and MEG) or spatial resolution (PET and fMRI). A combination of different techniques is therefore required in contemporary auditory research. One of the problems in comparing the EEG/MEG and fMRI methods, however, is the fMRI acoustic noise. In the present thesis, EEG and MEG in combination with behavioral techniques were used, first, to define the ERP correlates of automatic pitch discrimination across a wide frequency range in adults and neonates and, second, they were used to determine the effect of recorded acoustic fMRI noise on those adult ERP and ERF correlates during passive and active pitch discrimination. Pure tones and complex 3-harmonic sounds served as stimuli in the oddball and matching-to-sample paradigms. The results suggest that pitch discrimination in adults, as reflected by MMN latency, is most accurate in the 1000-2000 Hz frequency range, and that pitch discrimination is facilitated further by adding harmonics to the fundamental frequency. Newborn infants are able to discriminate a 20% frequency change in the 250-4000 Hz frequency range, whereas the discrimination of a 5% frequency change was unconfirmed. Furthermore, the effect of the fMRI gradient noise on the automatic processing of pitch change was more prominent for tones with frequencies exceeding 500 Hz, overlapping with the spectral maximum of the noise. When the fundamental frequency of the tones was lower than the spectral maximum of the noise, fMRI noise had no effect on MMN and P3a, whereas the noise delayed and suppressed N1 and exogenous N2. Noise also suppressed the N1 amplitude in a matching-to-sample working memory task. However, the task-related difference observed in the N1 component, suggesting a functional dissociation between the processing of spatial and non-spatial auditory information, was partially preserved in the noise condition. Noise hampered feature coding mechanisms more than it hampered the mechanisms of change detection, involuntary attention, and the segregation of the spatial and non-spatial domains of working-memory. The data presented in the thesis can be used to develop clinical ERP-based frequency-discrimination protocols and combined EEG and fMRI experimental paradigms.

Vuorovaikutus ääniterapiassa : Keskustelunanalyyttinen tutkimus harjoittelun rakenteesta, terapeutin antamasta palautteesta ja oppimisesta

This conversation analytical study analyses the interactional practices adopted by speech therapists and their clients during their training in voice therapy. This study also describes how learning takes place during the therapy process. In contrast to traditional voice therapy studies, change is examined here by using qualitative research methodology, namely conversation analysis. This study describes the structures of interaction in voice therapy, shows how the shortcomings in the client s performance are evaluated and corrected and finally, how the voice training sequence and the participation changes during therapy. The database consists of 51 videotaped voice therapy sessions from six clients with voice disorders. The analytic focus is on the practices in one voice training exercise of the trilled /r/. All the sequences of this exercise (in total 36) and all adjacency pairs within (N = 627) were transcribed and analysed in detail. This study shows that voice training consists of successive model imitation adjacency pairs. This adjacency pair works as a resource in voice training. Furthermore, the use of this particular adjacency pair is an institutional practice in all therapies in this study. The structure of interaction in voice training sequences resembles the practices found in aphasia therapy and in speech therapy of children, as well as the practices of educational and counselling interaction and physiotherapy. More than half of the adjacency pairs were expanded to three (or more) part structures as client s responses were typically followed by therapist s feedback. With their feedback turns, therapists: 1) maintain training practice, 2) evaluate the problem of client s performance, 3) deliver information, 4) activate the client to observe the performance and 5) assist her in correcting the performance. This study describes the four different ways that therapists help their clients to improve the performance after encountering a problem. The longitudinal data shows that learning in therapy is manifested in the changing participation. As clients learn to identify their voice features, they can participate in evaluating or correcting their performances by themselves. This study describes the recurrent professional practices of voice therapists and shows how the institutional commitments of voice therapy are managed in and through talk and interaction. The study also provides detailed description of the management of help in voice training. By describing the interaction in training sequences, this study expands the conception of voice rehabilitation and how it can be researched. The results demonstrate that the learning process and therapy outcomes can be assessed by analysing interaction in therapy. Moreover, this analysis lays the foundation for a novel understanding of the practices in speech therapy and for the development of speech therapy theory. By revealing the activities of interaction, it also makes it possible to discuss them explicitly with speech therapy students. Key words: voice therapy, conversation analysis, institutional interaction, learning, change in participation, feedback, evaluation, error correction, self-repair

Intercultural Learning and Hybridity in the Culture Laboratory

The number of immigrant students in vocational education and training is steadily increasing in Finland. This poses challenges for teachers and schools. This research focuses on emerging questions of intercultural learning in the context of immigrant training, and on a method the Culture Laboratory that was developed in an attempt to respond to the challenges. The main methodological and theoretical framework lies in cultural-historical activity theory, developmental work research, and in the concepts of the intercultural and hybridity. The empirical material consists of videotaped recordings of discussions in the Culture Laboratory. The five main research questions focused on the strengths and limitations of the Culture Laboratory as a tool for intercultural learning, the significance of disturbances in it, the potential of suggestions for intercultural learning, paper as a mediating artifact , and the concept of intercultural space. The findings showed that the Culture Laboratory offered a solid background for developing intercultural learning. The disturbances manifested revealed a multitude of scripts and activities. It was also suggested that the structure of expansive learning could start from externalization instead of internalization. The suggestions the participants made opened up a hybrid learning space for intercultural development, and offered a good springboard for new ideas. Learning in Paperland posed both challenges and opportunities for immigrant students, and different paper trails emerged. Intercultural space in the Culture Laboratory was a developmental zone in which a hybrid process of observing, comparing, and creating took place. Key words: intercultural learning, immigrant training, cultural-historical activity theory, developmental work research,

Corneal confocal microscopy predicts 4-year incident peripheral neuropathy in Type 1 diabetes

OBJECTIVE This study determined if deficits in corneal nerve fiber length (CNFL) assessed using corneal confocal microscopy (CCM) can predict future onset of diabetic peripheral neuropathy (DPN). RESEARCH DESIGN AND METHODS CNFL and a range of other baseline measures were compared between 90 nonneuropathic patients with type 1 diabetes who did or did not develop DPN after 4 years. The receiver operator characteristic (ROC) curve was used to determine the capability of single and combined measures of neuropathy to predict DPN. RESULTS DPN developed in 16 participants (18%) after 4 years. Factors predictive of 4-year incident DPN were lower CNFL (P = 0.041); longer duration of diabetes (P = 0.002); higher triglycerides (P = 0.023); retinopathy (higher on the Early Treatment of Diabetic Retinopathy Study scale) (P = 0.008); nephropathy (higher albumin-to-creatinine ratio) (P = 0.001); higher neuropathy disability score (P = 0.037); lower cold sensation (P = 0.001) and cold pain (P = 0.027) thresholds; higher warm sensation (P = 0.008), warm pain (P = 0.024), and vibration (P = 0.003) thresholds; impaired monofilament response (P = 0.003); and slower peroneal (P = 0.013) and sural (P = 0.002) nerve conduction velocity. CCM could predict the 4-year incident DPN with 63% sensitivity and 74% specificity for a CNFL threshold cutoff of 14.1 mm/mm2 (area under ROC curve = 0.66, P = 0.041). Combining neuropathy measures did not improve predictive capability. CONCLUSIONS DPN can be predicted by various demographic, metabolic, and conventional neuropathy measures. The ability of CCM to predict DPN broadens the already impressive diagnostic capabilities of this novel ophthalmic marker.

Structure of (6S,13bR)-1,2,3,5,6,13b-hexahydro-6-isopropyl-8H-pyrrolo[1',2':1,2]pyrazino[3,4,-b]quinazoline-5,8-dione

C17H19N302, monoclinic, P21, a = 5.382 (1), b = 17.534(4), c = 8.198(1)/L ,8 = 100.46(1) °, Z= 2, d,, = 1.323, dc= 1.299 Mg m-3, F(000) = 316, /~(Cu .Ka) = 0.618 mm -1. R = 0.052 for 1284 significant reflections. The proline-containing cispeptide unit which forms part of a six-membered ring deviates from perfect planarity. The torsion angle about the peptide bond is 3.0 (5) ° and the peptide bond length is 1.313 (5)A. The conformation of the proline ring is Cs-Cf~-endo. The crystal structure is stabilized by C-H... O interactions.