Amidinato- and triazenido-bridged binuclear complexes of palladium and platinum

The reaction of [M2Cl2(mu-Cl)(2)(PR3)(2)] (M=Pd or Pt; PR3=PEt3, PBu3, PMe2Ph, PMePh2) with lithium amidinate or sodium triazenide gave binuclear complexes containing amidinato- or triazenido-bridges, [M2Cl2(mu-ArNENAr)(2)(PR3)(2)] (E=CH, CMe or N). These complexes were characterized by elemental analysis and NMR (H-1, P-31 or Pt-195) data. The structures of two complexes, [(PdCl2)-Cl-2(mu-PhNC(Me)NPh)(2)(PMe2Ph)(2)] (10) and [Pt2Cl2(mu-PhNNNPh)(2)(PEt3)(2)] (11) were established by single crystal X-ray structural analyses. The Pt-195 NMR data Show coupling between two metal centers in the cis triazenido-bridged complex. The corresponding amidinate bridged complex does not show coupling. The role of the bridging ligand in mediating interaction between the metal centers is probed through Extended Huckel Theory (EHT) calculations. It is suggested that M-M interactions are primarily affected by the bridging ligands

Composite field approximations for ion traps with apertures on electrodes

This paper presents two approximate analytical expressions for nonlinear electric fields in the principal direction in axially symmetric (3D) and two dimensional (2D) ion trap mass analysers with apertures (holes in case of 3D traps and slits in case of 2D traps) on the electrodes. Considered together (3D and 2D), we present composite approximations for the principal unidirectional nonlinear electric fields in these ion traps. The composite electric field E has the form E = E-noaperture + E-aperture. where E-noaperture is the field within an imagined trap which is identical to the practical trap except that the apertures are missing and E-aperture is the field contribution due to apertures on the two trap electrodes. The field along the principal axis, of the trap can in this way be well approximated for any aperture that is not too large. To derive E-aperture. classical results of electrostatics have been extended to electrodes with finite thickness and different aperture shapes.E-noaperture is a modified truncated multipole expansion for the imagined trap with no aperture. The first several terms in the multipole expansion are in principle exact(though numerically determined using the BEM), while the last term is chosen to match the field at the electrode. This expansion, once Computed, works with any aperture in the practical trap. The composite field approximation for axially symmetric (3D) traps is checked for three geometries: the Paul trap, the cylindrical ion trap (CIT) and an arbitrary other trap. The approximation for 2D traps is verified using two geometries: the linear ion trap (LIT) and the rectilinear ion trap (RIT). In each case, for two aperture sizes (10% and 50% of the trap dimension), highly satisfactory fits are obtained. These composite approximations may be used in more detailed nonlinear ion dynamics Studies than have been hitherto attempted. (C) 2009 Elsevier B.V. All rights reserved.

Eigennamen in Pressetexten : Ein Vergleich zweier Online-Zeitungen

Tämä pro gradu -tutkielma vertailee korpuksen avulla erisnimien kvantitatiivista jakautumista luokkiin kahdessa saksalaisessa verkkolehdessä. Työn tavoitteena on selvittää, kuinka erisnimiä voidaan luokitella ja mitä eroja niiden avulla on havaittavissa lehtien raportoinnissa. Laajempana kehyksenä toimii kysymys siitä, voidaanko erisnimiä hyödyntäen hahmottaa lehtien sisältöjä. Korpus on kerätty Frankfurter Allgemeine Zeitungin ja Süddeutsche Zeitungin verkkolehtien http: //www.faz.net (FAZ) ja http://www.sueddeutsche.de (SZ) artikkeleista ajalta 2.11.2004-8.11.2004. Valitut sivustot edustavat Saksan arvostetuimpien päivittäisten, koko maan kattavien sanomaleh- tien verkkojulkaisuja. Näistä FAZ:ia pidetään konservatiivisena ja SZ:ia liberaalina lehtenä. Kumpikin korpus käsittelee USA:n presidentinvaaleja syksyllä 2004 ja sisältää hieman alle 30 000 sanaa noin 40 lehtiartikkelista. Aihesidonnaisen korpuksen valinta perustuu erityisesti siihen, että tutkimuksen päämääränä on saada erisnimien avulla selville, miltä osin FAZ ja SZ eroavat toisistaan käsitellessään samaa aihetta. Teoriaosassa käydään läpi saksalaisten verkkolehtien taustaa, työhön liittyviä tekstilingvistisiä teo- rioita sekä erisnimien erikoispiirteitä. Siinä käsitellään myös kolmea aiempaa, saksankielisen eris- nimitutkimuksen luokittelua ja yhtä englanninkielistä, kieliteknologian luokittelua. Näissä havaitut puutteet motivoivat yhdistelemään ja muuttamaan olemassa olevia luokitteluja tätä työtä varten. Uusi luokittelu sisältää neljä yläluokkaa (olentojen, maantieteelliset, instituutioden ja asioiden ni- met), jotka kaikki kattavat kahdesta yhdeksään alaluokkaa. Kummankin korpuksen erisnimet luo- kitellaan tämän perusteella. Kvantitatiivinen analyysi keskittyy ylä- ja alaluokkien vertailuun lehtien välillä. Lisäksi se kattaa sekä kummankin aineiston että pääluokkien frekventimpien sanojen tarkastelun. Vaikka FAZ ja SZ käyttivätkin pääosin samoja erisnimiä raportoinnissaan, voidaan lehtien välillä osoittaa selkeitä eroja alaluokkien kohdalla ja vähäisiä eroja erisnimien jakautumisessa yläluokkiin. chi2 -testin näytti kuitenkin, että erisnimien jakautuminen yläluokkiin on lehtisidonnaista. Siksi voidaan väittää, että muun muassa valittu media vaikuttaa erisnimivalintoihin. Erisnimien frekvenssit antavat ymmärtää, että SZ raportoisi monipuolisemmin kuin FAZ, joka käyttää erisnimiä keskitetymmin. SZ:in aineiston erisnimiä yhdistää eurooppalainen näkökulma vaaleihin, kun taas FAZ pyrkii tuomaan esille tapahtumia USA:n eri osavaltioissa. Niin lehdissä mainitut henkilöiden kuin instituutioden nimet tukevat tätä väitetettä. SZ korostaa maantieteellisesti kaupunkien merkitystä, FAZ osavaltioiden. Saadut tulokset osoittavat, että tämänkaltaisen erisnimitutkimuksen soveltaminen lehtiteksteihin on mahdollista. Luokitellut erisnimet heijastavat osittain käsiteltyjen aineistojen sisältöä ja paljastavat raportoinnin painopisteistä.

Suomi kasvitieteen kieleksi : Elias Lönnrot termistön kehittäjänä

The development of botanical Finnish: Elias Lönnrot as the creator of new terminology In the 19th century the Finnish language was intentionally developed to meet the demands of civilised society and Finnish-language science. The development of the language involved several people from different fields of science. This study examines this enormous project in the field of botany. By which methods were scientific terms formed, and for which reasons were those terms used? Why has a certain word been chosen to represent a particular concept? The material of this study is the terminology of plant morphology in Finnish that Elias Lönnrot developed in the middle of the 19th century. The terms of plant morphology denote and describe the parts of the plant and the relationships between those parts. For instance, the terms emi pistill , hede stamen , terälehti petal and verholehti sepal , which are nowadays familiar in the general language, were used for the first time in Lönnrot s texts. The study integrates the methods of lexicology and terminology. In lexicology, the word and its various meanings serve as the focus, whereas the theory of terminology focuses on the concept and concept systems. A new, consciously developed terminology can be understood through the old, familiar vocabulary and structures as well as through the new, logical term system. Lönnrot s botanical terminology can be divided into three groups depending on their origin: 1) 19% of all terms have been accepted from the existing vocabulary and used in their original meanings, 2) 11% of all terms have been chosen from the existing vocabulary and used in the new, specific botanical meanings, and 3) 70% of all terms have been created on the basis of the existing vocabulary and used in the new, specific botanical meanings. Therefore, the study reveals that domestic materials primarily morphosemantic neologisms form the Finnish terminology of plant morphology. Characteristic of Lönnrot s botanical terms is the utilisation of the vocabulary of various Finnish dialects and particular repeating elements. Repeating elements include, for example, the prefixes that come from botanical Latin or Swedish as well as the particular Finnish derivation types. Such structures form term systems that reflect scientific concept systems. Two thirds of the created new words are formed loosely or precisely according to either Latin or Swedish terms; one third is formed completely differently from its equivalents in the foreign languages. Approximately half of the chosen terms are formed differently from the Latin and Swedish terms. It is worth noting that many loan translations use rare vocabulary from Finnish dialects as equivalents to foreign parts of terms. Lönnrot aimed to inspire scientific terminology with Finland s own language, thus making scientific text accessible to the Finnish agricultural population.

Microbial ecology of the equine hindgut during oligofructose-induced laminitis

Alimentary carbohydrate overload is a significant cause of laminitis in horses and is correlated with drastic shifts in the composition of hindgut microbiota. Equine hindgut streptococcal species (EHSS), predominantly Streptococcus lutetiensis, have been shown to be the most common microorganisms culturable from the equine caecum prior to the onset of laminitis. However, the inherent biases of culture-based methods are estimated to preclude up to 70% of the normal caecal microbiota. The objective of this study was to evaluate bacterial population shifts occurring in the equine caecum throughout the course of oligofructose-induced laminitis using several culture-independent techniques and to correlate these with caecal lactate, volatile fatty acid and degrees of polymerization 3-7 fructo-oligosaccharide concentrations. Our data conclusively show that of the total microbiota present in the equine hindgut, the EHSS S. lutetiensis is the predominant microorganism that proliferates prior to the onset of laminitis, utilizing oligofructose to produce large quantities of lactate. Population shifts in lactobacilli and Escherichia coli subpopulations occur secondarily to the EHSS population shifts, thus confirming that lactobacilli and coliforms have no role in laminitis. A large, curved, Gram-negative rod previously observed during the early phases of laminitis induction was most closely related to the Anaerovibrio genus and most likely represents a new, yet to be cultured, genus and species. Correlation of fluorescence in situ hybridization and quantitative real-time PCR results provide evidence supporting the hypothesis that laminitis is associated with the death en masse and rapid cell lysis of EHSS. If EHSS are lysed, liberated cellular components may initiate laminitis.

Seasonal variations in the body composition of lightweight rowers

OBJECTIVE To monitor the seasonal body composition alterations in 18 lightweight rowers (six females, 12 males) across a rowing season incorporating preseason, early competition, competition, and postseason. METHODS Subject age was 23.1 (SD 4.5) years, height 170.8 (5.6) cm (female, 23.5 (3.5) years, 180.5 (2.7) cm (male). Body weight, fat mass, and fat-free mass (FFM) were assessed using dual energy x ray absorptiometry (DXA-L Lunar) and skinfold techniques. Weight control techniques were documented before major regattas by a questionnaire. RESULTS Female body weight was reduced from 61.3 (2.9) to 57.0 (1.1) kg (5.9%), while male body weight was reduced from 75.6 (3.1) to 69.8 (1.6) kg (7.8%) preseason to competition season respectively. These body weight reductions were mirrored by a significant reduction in fat mass as indicated by the sum of skinfolds [female seven sites: 80.9 (8.1) to 68.2 (11.8) mm; male eight sites: 54.2 (8.7) to 41.8 (4.8) mm], percentage body fat [female 22.1 (1.0) to 19.7 (2.4)%; male 10.0 (0.9) to 7.8 (0.8)%], and total fat [female 12.5 (5.2) to 10.9 (1.4) kg; male 7.3 (1.9) to 5.6 (1.8) kg] (DXA). In contrast, no changes were observed in FFM despite a season of intensive rowing training. Seasonal body weight control was achieved through reduced total energy and dietary fat intakes. Acute body weight reductions were achieved by exercise in 73.3% of participants, food restriction in 71.4%, and fluid restrictions in 62.9%. CONCLUSIONS Seasonal body weight alterations in lightweight rowers are in response to a significant reduction in fat mass. However, the weight restrictions appear to be limiting an increase in FFM which could be beneficial to rowing performance.

Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.

Nomenclatural corrections to Australian species of Cricotopus (Wulp) (Diptera; Chironomidae)

Our attention has been drawn to lapsi and errors in a recent publication in this journal concerning Cricotopus Wulp (Diptera: Chironomidae) (Drayson et al., 2015).

Synthesis of Azo Coupled Crown Ethers Containing Transition Metal and other Chromophoric Environments and Their Ion Complexation Properties

The crown ethers, 2,3-benzo-1,4,7,10,13-pentaoxa-cyclopentadeca-2-ene and 2,3, ll,12-dibenzo-l,4,7,10,13,16-hexaoxscyclooctadeca-2,11-diene are incorporated into H,N'-ethylenebis(acetylacetoneimino) nickel(II) and copper(II), phenol, and β-naphthol by diazo coupling reactions. The selective nature of the coupling reaction has-been demonstrated by the isolation of both asymmetric mono- and symmetric bis(glyoxalarylcrownhydrazoneimino) metal(II) complexes. An interesting binuclear complex containing two intramolecularly rearranged (glyoxal-hydrazonearylimino) metal(II) groups joined by 18-crown-6 result8 when bis(arenediazonium)-18-crown-6 is coupled with the metal(I1) Schiff bases. The substituted ethers form cationic salts with NaClO4, KCNS, NH4CNS, 14g(CNS)2 and Ca(CNS)2. All the synthesised ethers exhibit ion selectivity sequence as K+ > Na+ and Ca2+ > Mg2+.

A new mixed-matrix membrane for DMFCs

A new mixed-matrix membrane based on stabilized phosphotungstic acid (PTA) incorporated to chitosan (CS)-hydroxy ethyl cellulose (HEC) for application in direct methanol fuel cells (DMFCs) is reported. Membranes are characterised using Fourier Transform Spectroscopy (FTIR), Thermo-Gravimetric Analysis (TGA), Scanning Electron Microscopy (SEM) and their mechanical properties are evaluated. The PTA content in the CS-HEC blend and its influence on proton conductivity, water/methanol sorption, and methanol cross-over in the DMFC is studied. The DMFC with 3 wt. % stabilized PTA-CS-HEC mixed-matrix membrane delivers peak power-density of 58 mW/cm(2) at a load current-density of 210 mA/cm(2) with a lower methanol cross-over than that observed for a DMFC operating with a Nafion membrane electrolyte.

Charge distribution in and dipole moments of some aliphatic alcohols

Using the treatment of Smith, et al.,1 charge distributions in several aliphatic alcohols and consequently their dipole moments have been evaluated. The dipole moments of trichloroethanol (2.04 D) and 1,3-dichloropropan-2-ol (2.11 D) have been measured in benzene solution at 35°. The results of evaluation and measurements are interpreted in terms of the occurrence of intramolecular interaction between the hydroxyl hydrogen and an acceptor atom X (halogen or oxygen) at the β-carbon atom.

Factor V Leiden as risk factor for pregnancy complications : Epidemiological study of Finnish women

Factor V Leiden (FV Leiden) is the most common inherited thrombophilia in Caucasians increasing the risk for venous thrombosis. Its prevalence in Finland is 2-3%. FV Leiden has also been associated with several pregnancy complications. However, the importance of FV Leiden as their risk factor is unclear. The aim of the study was to assess FV Leiden as a risk factor for pregnancy complications in which prothrombotic mechanisms may play a part. Specifically, the study aimed to assess the magnitude of the risk, if any, associated with FV Leiden for pregnancy-associated venous thrombosis, pre-eclampsia, unexplained stillbirth, and preterm birth. The study was conducted as a nested case-control study within a fixed cohort of 100,000 consecutive pregnant women in Finland. The study was approved by the ethics committee of the Finnish Red Cross Blood Service and by the Ministry of Social Affairs and Health. All participants gave written informed consent. Cases and controls were identified by using national registers. The diagnoses of the 100,000 women identified from the National Register of Blood Group and Blood Group Antibodies of Pregnant Women were obtained from the National Hospital Discharge Register. Participants gave blood samples for DNA tests and filled in questionnaires. The medical records of the participants were reviewed in 49 maternity hospitals in Finland. Genotyping was performed in the Finnish Genome Center. When evaluating pregnancy-associated venous thrombosis (34 cases, 641 controls), FV Leiden was associated with 11-fold risk (OR 11.6, 95% CI 3.6-33.6). When only analyzing women with first venous thrombosis, the risk was 6-fold (OR 5.8, 95% CI 1.6-21.8). The risk was increased by common risk factors, the risk being highest in women with FV Leiden and pre-pregnancy BMI over 30 kg/m2 (75-fold), and in women with FV Leiden and age over 35 years (60-fold). When evaluating pre-eclampsia (248 cases, 679 controls), FV Leiden was associated with a trend of increased risk (OR 1.7, 95% CI 0.8-3.9), but the association was not statistically significant. When evaluating unexplained stillbirth (44 cases, 776 controls), FV Leiden was associated with over 3-fold risk (OR 3.8, 95% CI 1.2-11.6). When evaluating preterm birth (324 cases, 752 controls), FV Leiden was associated with over 2-fold risk (OR 2.4, 95% CI 1.3-4.6). FV Leiden was especially associated with late preterm birth (32-36 weeks of gestation), but not with early preterm birth (< 32 weeks of gestation). The results of this large population-based study can be generalized to Finnish women with pregnancies continuing beyond first trimester, and may be applied to Caucasian women in populations with similar prevalence of FV Leiden and high standard prenatal care.

Enhanced photodynamic effect of cobalt(III) dipyridophenazine complex on thyrotropin receptor expressing HEK293 cells

Ternary cobalt(III) complexes CoL(B)] (1-3) of a trianionic tetradentate phenolate-based ligand (L) and phenanthroline bases (B), viz. 1,10-phenanthroline (phen in 1), dipyridoquinoxaline (dpq in 2) and dipyridophenazine (dppz in 3) are synthesized, characterized from X-ray crystallographic, analytical and spectral techniques, and their utility in photodynamic therapy (PDT) of thyroid diseases caused by TSH receptor dysfunction is probed. The complexes display a visible spectral band within the PDT spectral window at similar to 690 nm. Photodynamic potential was estimated through DNA cleavage activity of the dpq and dppz complexes in UV-A light of 365 nm and red light of 676 nm. The reactions proceed via the hydroxyl radical pathway. The complexes retain their DNA photocleavage activity in red light under anaerobic conditions, a situation normally prevails in hypoxic tumor core. Investigation into the photocytotoxic potential of these complexes showed that the dppz complex 3 is approximately 4-fold more active in the HEK293 cells expressing human thyrotropin receptor (HEK293-hTSHR) than in the parental cell line and has an insignificant effect on an unrelated human cervical carcinoma cell line (HeLa). Photoexcitation of complex 3 in HEK293-hTSHR cells leads to damage hTSHR as evidenced from the decrease in cAMP formation both in absence and presence of hTSH and decrease in the TSHR immunofluorescence with a concomitant cytoplasmic translocation of the membrane protein, cadherin. The involvement of hTSHR is evidenced from the ability of complex 3 to bind to the extracellular domain of hTSHR (hTSHR-ECD) with a K-d value of 81 nM and from the photocleavage of hTSHR-ECD.

The influence of lone-pair repulsions on C–C bond lengths: a critical evaluation of the experimental and theoretical evidence

X-Ray structural data, as well as semiempirical and ab initio molecular orbital calculations, reveal no systematic and substantial difference between the C–C bond lengths of cis and trans 1,2-diketones. Additional results on various conformations of 1,2-diimines and 1,2-dithiones follow the same pattern. Therefore, lone-pair repulsions cannot be implicated in the observed lengthening of C–C bonds in isatin and several related molecules. Conjugation in these systems occurs peripherally avoiding the participation of the central C–C bond. Negative hyperconjugative interaction between the oxygen lone pairs and the adjacent C–C σ* orbital is suggested to be the principal reason for the relatively long C–C bond in diketones. This effect is found in both the cis and trans conformations.