New metallomolecular wires based on carbon-rich bridging systems: a systematic study

This dissertation presents and discusses the preparation of molecular wires (MW) candidates that would then be probed for electron transfer properties. These wires are bridged by 1,4-diethynylbenzene derivatives with alkoxy side chains with palladium and ruthenium metal complex termini. Characterization of these compounds was performed by usual spectroscopic techniques like 1H, 13C{1H} and 31P{1H} NMR, MS, FTIR and UV-Vis as well as by cyclic voltammetry which allowed classifying the candidates in the Robin–Day system and determination of bridges side chain and length effects on electronic transport. Preparation of the 1,4-diethynylbenzene derivatives was done with synthetic pathways that relied heavily in palladium catalyzed cross-couplings (Sonogashira). A family of single ringed 1,4-diethynylbenzene ligands with different length alkoxy side chains (OCH3, OC2H5, OC7H15) was thus prepared allowing for the influence of these ring decorations to be assessed. The ruthenium binuclear rods showed communication between metal centres only when the shorter ligands were used whereas the longer Ru complexes showed only one redox pair in CV studies which is in agreement to non-communicating metal centres. Cyclic voltammetry studies show irreversible one wave processes for palladium dinuclear complexes, making these rods function as molecular insulators. Fluorescence decay studies performed on the prepared compounds (ligands and complexes) show a pattern of decreasing decay times upon coordination to the metal centres which can due to ligand charge redistribution upon coordination leading to non-radiative relaxation paths. Regarding the X-ray structures, two new ligand related structures were obtained as well as new structure for a palladium rod. The effect of the side chains was observed to be important to the wires’ electronic properties when comparing with the analogues without a side chain. The effect brought by longer chains is nevertheless almost negligible.

Multifactor effects and evidence of potential interaction between complement factor H Y402H and LOC387715 A69S in age-related macular degeneration.

BACKGROUND: Variants in the complement cascade genes and the LOC387715/HTRA1, have been widely reported to associate with age-related macular degeneration (AMD), the most common cause of visual impairment in industrialized countries. METHODS/PRINCIPAL FINDINGS: We investigated the association between the LOC387715 A69S and complement component C3 R102G risk alleles in the Finnish case-control material and found a significant association with both variants (OR 2.98, p = 3.75 x 10(-9); non-AMD controls and OR 2.79, p = 2.78 x 10(-19), blood donor controls and OR 1.83, p = 0.008; non-AMD controls and OR 1.39, p = 0.039; blood donor controls), respectively. Previously, we have shown a strong association between complement factor H (CFH) Y402H and AMD in the Finnish population. A carrier of at least one risk allele in each of the three susceptibility loci (LOC387715, C3, CFH) had an 18-fold risk of AMD when compared to a non-carrier homozygote in all three loci. A tentative gene-gene interaction between the two major AMD-associated loci, LOC387715 and CFH, was found in this study using a multiplicative (logistic regression) model, a synergy index (departure-from-additivity model) and the mutual information method (MI), suggesting that a common causative pathway may exist for these genes. Smoking (ever vs. never) exerted an extra risk for AMD, but somewhat surprisingly, only in connection with other factors such as sex and the C3 genotype. Population attributable risks (PAR) for the CFH, LOC387715 and C3 variants were 58.2%, 51.4% and 5.8%, respectively, the summary PAR for the three variants being 65.4%. CONCLUSIONS/SIGNIFICANCE: Evidence for gene-gene interaction between two major AMD associated loci CFH and LOC387715 was obtained using three methods, logistic regression, a synergy index and the mutual information (MI) index.

Should the standard dimethyl sulfoxide concentration be reduced? Results of a European Group for Blood and Marrow Transplantation prospective noninterventional study on usage and side effects of dimethyl sulfoxide.

BACKGROUND Dimethyl sulfoxide (DMSO) is essential for the preservation of liquid nitrogen-frozen stem cells, but is associated with toxicity in the transplant recipient. STUDY DESIGN AND METHODS In this prospective noninterventional study, we describe the use of DMSO in 64 European Blood and Marrow Transplant Group centers undertaking autologous transplantation on patients with myeloma and lymphoma and analyze side effects after return of DMSO-preserved stem cells. RESULTS While the majority of centers continue to use 10% DMSO, a significant proportion either use lower concentrations, mostly 5 or 7.5%, or wash cells before infusion (some for selected patients only). In contrast, the median dose of DMSO given (20 mL) was much less than the upper limit set by the same institutions (70 mL). In an accompanying statistical analysis of side effects noted after return of DMSO-preserved stem cells, we show that patients in the highest quartile receiving DMSO (mL and mL/kg body weight) had significantly more side effects attributed to DMSO, although this effect was not observed if DMSO was calculated as mL/min. Dividing the myeloma and lymphoma patients each into two equal groups by age we were able to confirm this result in all but young myeloma patients in whom an inversion of the odds ratio was seen, possibly related to the higher dose of melphalan received by young myeloma patients. CONCLUSION We suggest better standardization of preservation method with reduced DMSO concentration and attention to the dose of DMSO received by patients could help reduce the toxicity and morbidity of the transplant procedure.

Repeatability, reproducibility, and accuracy of a novel pushbroom hyperspectral system

This study analyzes the repeatability, reproducibility and accuracy of a new hyperspectral system based on a pushbroom sensor as a means of measuring spectral features and color of materials and objects. The hyperspectral system consisted of a CCD camera, a spectrograph and an objective lens. An additional linear moving system allowed the mechanical scanning of the complete scene. A uniform overhead luminaire with daylight configuration was used to irradiate the scene using d:45 geometry. We followed the guidelines of the ASTM E2214-08 Standard Practice for Specifying and Verifying the Performance of Color-Measuring Instruments that define the standards and latest multidimensional procedures. The results obtained are analyzed in-depth and compared to those recently reported by other authors for spectrophotometers and multispectral systems. It can be concluded that hyperspectral systems are reliable and can be used in the industry to perform spectral and color readings with a high spatial resolution.

Resurssiperusteinen ajattelu ammattijoukkueurheilussa: NHL-joukkueiden kyky tunnistaa suorituskykyä parantavat henkilöstöresurssit

Tutkijoita on viime vuosina yhä enenevissä määrin kiinnostanut johtamisen ja johtajuuden tutkimuksen eri teorioiden soveltaminen urheiluympäristössä. Tämä pätee myös kestävän kilpailuedun ja resurssiperusteisen ajattelun tutkimukseen. Urheilullisen menestyksen ylläpitäminen on ammattiurheilujoukkueiden kiinnostavuuden ja hyvän taloudellisen tuloksen kannalta ensiarvoisen tärkeää. Huono urheilullinen menestys voi tarkoittaa myös suurta menetystä joukkueiden kykyyn luoda tuloja, sillä kannattajien sekä sponsoreiden kiinnostus seuraa kohtaan voi laskea. Valmentajanvaihdokset eri urheilulajeissa ovat kiinnostaneet niin urheilu- kuin strategisen johtamisen tutkijoita jo pitkään, mutta niiden vaikutuksista joukkueiden suorituskykyyn ei ole päästy yhteisymmärrykseen. Tämän tutkielman tarkoituksena on selvittää, miten johtajavaihdosten ilmiö näkyy NHL-joukkueissa, ja millaisia vaikutuksia sillä on joukkueiden suorituskykyyn. Tämän lisäksi selvitetään kuinka hyvin NHL-joukkueiden seurajohto on onnistunut omien henkilöstöresurssiensa kyvykkyyden ja tehokkuuden arvioimisessa tehdessään päätöksen vaihtaa valmentajaa. Tässä tutkielmassa tutkittiin yhteensä 19 kesken kauden tapahtunutta valmentajanvaihdosta jääkiekon NHL:ssä kausien 2005–2006 ja 2014–2015 välisenä aikana. Valmentajien tehokkuutta hyödyntää käytössään olevia resursseja mitattiin data envelopment analysis (DEA) -menetelmän avulla. Tutkielman tuloksista käy ilmi, että valmentajanvaihdoksen myötä joukkueiden suorituskyky parani lähes poikkeuksetta. Suorituskyky oli myös parempaa, kun sitä verrattiin vaihdosta edeltäneeseen kauteen, ja se parani edelleen vaihdosta seuranneella kaudella. Saatujen tulosten valossa voidaan siis todeta, että NHL:ssä valmentajan vaihtamisella kesken kauden on positiivista vaikutusta joukkueen suorituskykyyn. Vaikutus on positiivista ainakin silloin, kun vaihdettu valmentaja sekä tämän korvaaja ovat molemmat saaneet valmentaa joukkuetta vähintään yhden kokonaisen kauden ajan ennen vaihdoskautta tai sen jälkeen. Tulokset myös viittaavat siihen, että huonon urheilullisen menestyksen pohjalta tehdyt vaihdospäätökset ovat perusteltuja. Näin ollen voidaan todeta, että NHL-joukkueen johto on pääsääntöisesti onnistunut tunnistamaan tehottoman henkilöstöresurssin ja kyennyt korvaamaan sen kyvykkyyksiltään paremmalla resurssilla. Tutkielman tuloksia ei kuitenkaan voida yleistää yli sarja- ja lajirajojen, sillä jokaisella urheilusarjalla ja -lajilla on omat erityispiirteensä, minkä takia niiden keskinäinen vertailu ei ole mielekästä.

Spatial multicriteria decision analysis to potential beekeeping assessment. Case study: Montesinho Natural Park (Portugal)

The Multicriteria decision analysis is a tool to support decision-making in the identification of areas with the utmost beekeeping potential. This paper design a GIS multicriteria approach to assess the beekeeping potential. The development of a conceptual model structure requires the participation of stakeholders and experts in that process. The spatial Multicriteria Decision Analysis (MCDA) allowed defining the potential beekeeping map. The resulting maps can be used by the beekeepers associations to easily select the more suitable areas for the apiaries location or relocation and avoid prohibited areas by legal requirements.