Diverting Hydrogenations with Wilkinson's Catalyst towards Highly Reactive Rhodium(I) Species.

The addition of Barton's base has a dramatic effect on the classic rhodium(III)-mediated hydrogenations promoted by Wilkinson's catalyst. Following the initial oxidative addition, a barrierless reductive elimination of HCl from the traditional rhodium(III) intermediates instantly produces a rhodium(I) monohydride species, which is remarkably reactive in the hydrogenation of several internal alkynes and functionalized trisubstituted alkenes. The direct formation of this species is unprecedented upon addition of molecular hydrogen and its catalytic potential has been hitherto barely explored.

Monosomy of chromosome 17 in breast cancer during interpretation of HER2 gene amplification.

Monosomy of chromosome 17 may affect the assessment of HER2 amplification. Notably, the prevalence ranges from 1% up to 49% due to lack of consensus in recognition. We sought to investigate the impact of monosomy of chromosome 17 to interpretation of HER2 gene status.

Life-threatening coronary disease is prevalent in patients with stenosing carotid artery disease.

Background: Atherosclerosis affects several vascular trees systemically and though surgical plaque removal diminishes the risk of stroke in patients with carotid stenosis, they still face a risk of other atherothrombotic complications like myocardial infarction and premature death.

Aims And/or Hypothesis: This study was designed to reveal the long-term risk of death and atherothrombotic events following carotid endarterectomy.

Methods: Eighty-nine previously (1997-2000) endarterectomized carotid patients (56-92 years) were followed up to 15·2 years.

Synthesis, aromaticity and photophysical behaviour of ferrocene- and ruthenocene-appended semisynthetic chlorin derivatives.

Two novel synthetic strategies to covalently link a metallocene electron-donor unit to a chlorin ring are presented. In one approach, pyropheophorbide a is readily converted into its 13(1) -ferrocenyl dehydro derivative by nucleophilic addition of the ferrocenyl anion to the 13(1) -carbonyl group. In another approach, the corresponding 13(1) -pentamethylruthenocenyl derivative is synthesised from 13(1) -fulvenylchlorin by a facile ligand exchange/deprotonation reaction with the [RuCp*(cod)Cl] (Cp*=pentamethylcyclopentadienyl; cod=1,5-cyclooctadiene) complex.

HOXA10 controls proliferation, migration and invasion in oral squamous cell carcinoma.

Although HOX genes are best known for acting in the regulation of important events during embryogenesis, including proliferation, differentiation and migration, alterations in their expression patterns have been frequently described in cancers. In previous studies we analyzed the expression profile of the members of the HOX family of homeobox genes in oral samples of normal mucosa and squamous cell carcinoma (OSCC) and identified differently expressed genes such as HOXA10. The present study aimed to validate the increased expression of HOXA10 in OSCCs, and to investigate the effects arising from its knockdown in OSCC cells.

The significance of gender in fetuses with increased nuchal translucency: pregnancy outcomes and long-term outcomes of children.

Objective: We aim to study the gender impact on the pregnancy outcome and on the long-term outcome of children after increased fetal nuchal translucency.

Method: All singleton pregnancies with increased nuchal translucency (≥3 mm until 1 March 2004 and ≥95th percentile thereafter) referred to Helsinki University Hospital from 2002 to 2007 with known gender and normal sex chromosomes were included. The pregnancy outcome (miscarriage, termination of pregnancy, perinatal death or delivery of a healthy/unhealthy child) and the long-term outcome (structural defects or neurodevelopmental impairment) were recorded from hospital databases and national registers.

Dinitrogen fixation by legume shade trees and direct transfer of fixed N to associated cacao in a tropical agroforestry system.

Natural abundance of (15)N (δ (15)N) was determined in bulk soil, rhizospheric soil and vegetation in an organically managed cacao (Theobroma cacao L.) plantation with Inga edulis Mart. legume trees (inga) as the principal shade for studying the nitrogen (N) cycle in the system.

Photoinduced charge transfer in a conformational switching chlorin dimer-azafulleroid in polar and nonpolar media.

In the present study, a biomimetic reaction center model, that is, a molecular triad consisting of a chlorin dimer and an azafulleroid, is synthesized and its photophysical properties are studied in comparison with the corresponding molecular dyad, which consists only of a chlorin monomer and an azafulleroid. As evidenced by (1) H NMR, UV/Vis, and fluorescence spectroscopy, the chlorin dimer-azafulleroid folds in nonpolar media into a C2 -symmetric geometry through hydrogen bonding, resulting in appreciable electronic interactions between the chlorins, whereas in polar media the two chlorins diverge from contact. Femtosecond transient absorption spectroscopy studies reveal longer charge-separated states for the chlorin dimer-azafulleroid; ≈1.

Rapid autoxidation forms highly oxidized RO2 radicals in the atmosphere.

Gas-phase oxidation routes of biogenic emissions, mainly isoprene and monoterpenes, in the atmosphere are still the subject of intensive research with special attention being paid to the formation of aerosol constituents. This laboratory study shows that the most abundant monoterpenes (limonene and α-pinene) form highly oxidized RO2 radicals with up to 12 O atoms, along with related closed-shell products, within a few seconds after the initial attack of ozone or OH radicals. The overall process, an intramolecular ROO→QOOH reaction and subsequent O2 addition generating a next R'OO radical, is similar to the well-known autoxidation processes in the liquid phase (QOOH stands for a hydroperoxyalkyl radical).

Impact of environmental stress on biochemical parameters of bacteria reducing chromium.

Chromium pollution is produced in connection with industrial processes like in tanneries. It has been suggested that bioremediation could be a good option for clean up. The stress effect of variable chromate levels, pHs and growth temperatures on biochemical parameters of two Cr(VI) reducing bacterial strains Pseudomonas aeruginosa Rb-1 and Ochrobactrum intermedium Rb-2 was investigated.

Kindlin-3 in the immune system.

Kindlin-3 is a member of the kindlin family of focal adhesion proteins which bind to integrin beta-chain cytoplasmic domains to regulate integrin function. In contrast to kindlin-1 and kindlin-2 proteins, kindlin-3 is expressed mainly in the hematopoietic system. Mutations in kindlin-3 result in the rare genetic disorder, leukocyte adhesion deficiency type III (LAD-III), which is characterized by bleeding and recurrent infections due to deficient beta1, beta2 and beta3 integrin activation in platelets and leukocytes.

Double Photoinduced Jahn-Teller Distortion of Tetrahedral Au Sn Complexes.

Tetrahedral Au complexes [L Au(SnCl )] (L=PMe (1), PMe Ph (2), PMePh (3), and PPh (4)) were prepared by treatment of the [(tht)Au(SnCl )] (tht=tetrahydrothiophene) complex with three equivalents of the corresponding tertiary phosphine. The crystal structures of complexes 1-4 have been determined through X-ray diffraction studies showing, in all cases, [SnCl ] fragments covalently bonded to the corresponding [Au(PR ) ] units, which leads to a tetrahedral coordination environment for gold. Complexes 3 and 4 show phosphorescence in the solid state at room temperature and 77 K that is largely redshifted relative to the free [Au(PR ) ] and [SnCl ] counterparts.

Genetic and life-history changes associated with fisheries-induced population collapse.

Over the recent years, growing number of studies suggests that intensive size-selective fishing can cause evolutionary changes in life-history traits in the harvested population, which can have drastic negative effects on populations, ecosystems and fisheries. However, most studies to date have overlooked the potential role of immigration of fish with different phenotypes as an alternative plausible mechanism behind observed phenotypic trends. Here, we investigated the evolutionary consequences of intensive fishing simultaneously at phenotypic and molecular level in Eurasian perch ( L.

Phylogeography of the ant Myrmica rubra and its inquiline social parasite.

Widely distributed Palearctic insects are ideal to study phylogeographic patterns owing to their high potential to survive in many Pleistocene refugia and-after the glaciation-to recolonize vast, continuous areas. Nevertheless, such species have received little phylogeographic attention. Here, we investigated the Pleistocene refugia and subsequent postglacial colonization of the common, abundant, and widely distributed ant Myrmica rubra over most of its Palearctic area, using mitochondrial DNA (mtDNA).

Interactions of the HIV/SIV pathogenicity factor Nef with SH3 domain-containing host cell proteins.

A bewildering number of host cell proteins associated with Nef can be found in the literature and in the public protein interaction databases. However, only in a few of these cases, including binding of Nef to certain Src homology-3 (SH3) domain proteins, is the interaction understood in any molecular detail or even known to be direct. Indeed, SH3 binding capacity by Nef is required for many of the other protein interactions to take place, suggesting that a large proportion of the latter is indirectly coupled to Nef via an SH3 protein.

Context-dependent effects of induced resistance under co-infection in a plant-pathogen interaction.

The ability of a parasite strain to establish and grow on its host may be drastically altered by simultaneous infection by other parasite strains, and dynamics under multiple infection have been suggested to be a major force driving pathogen evolution. Here, I studied whether hosts' induced defenses mediate dynamics of multiple infection of the fungal pathogen, Podosphaera plantaginis, infecting Plantago lanceolata. A laboratory study of sequential infections, where interaction between pathogen strains was prevented, showed that ability to establish remained unaffected, but prior infection elevates the host's resistance to the degree that subsequent infection development is significantly reduced.

Barriers to medication counselling for people with mental health disorders: a six country study.

Unlabelled: Provision of medication information may improve adherence and prevent medication related problems. People with mental health disorders commonly receive less medication counselling from pharmacists than people with other common long term and persistent disorders.

Objective: The objective of this study was to compare and contrast barriers pharmacy students perceive toward providing medication counselling for people with mental health disorders in Australia, Belgium, Estonia, Finland, India and Latvia.

Immigration within European Union - Does health immigration make a difference in analgesic use?

Unlabelled: European integration has facilitated the emigration inside Europe and it has been predicted that the amount of immigrants in Southern European countries will increase in the future. As these people age and their morbidity increases, they will demand more services from local health care than immigrants do at the moment. The aim of this study is to determine the amount of Finnish people who have moved to Spain for health reasons (health immigrants) and whether their health service and analgesic usage patterns differed from those of non-health immigrants.

The contribution of musculoskeletal disorders and physical workload to socioeconomic inequalities in health.

Objectives: The objective of the study was to examine whether the association of physical workload with musculoskeletal disorders might explain occupational social class inequalities in self-rated health.

Methods: Participants of the study were 40-60 years old employees of the City of Helsinki. The data (n = 3740) were derived from several sources, including mail survey designed by the researchers and health check-ups carried out by occupational health care.

Planning optimal measurements of isotopomer distributions for estimation of metabolic fluxes.

Motivation: Flux estimation using isotopomer information of metabolites is currently the most reliable method to obtain quantitative estimates of the activity of metabolic pathways. However, the development of isotopomer measurement techniques for intermediate metabolites is a demanding task. Careful planning of isotopomer measurements is thus needed to maximize the available flux information while minimizing the experimental effort.

Sensitive pattern discovery with 'fuzzy' alignments of distantly related proteins.

Motivation: Evolutionary comparison leads to efficient functional characterisation of hypothetical proteins. Here, our goal is to map specific sequence patterns to putative functional classes. The evolutionary signal stands out most clearly in a maximally diverse set of homologues.

Expression of mRNAs for neurotrophins and their receptors in developing rat heart.

Because the neurotrophic system has not been systematically studied in developing heart, we studied the expression of mRNAs for neurotrophins and their high- and low-affinity receptors by radioactive in situ hybridization in the rat heart from embryonic day 9 (E9) to parturition. The neurotrophin-3 (NT-3) transcripts were seen in the group of Leu-7 immunoreactive cells in the ventricular region from E11 to parturition, suggesting that NT-3 is expressed in the part of the developing conduction system, mRNAs for truncated trk receptors, trkC.TK- and trkB.

Magnetic fields and leukemia--risk for adults living close to power lines.

The objective of this study was to investigate the risk of leukemia from magnetic field exposure among Finnish adults living close to high-voltage power lines. The cohort study included 383700 Finnish people having lived in 1970-1989 within 500 m of overhead power lines of 110-400 kV in a magnetic field calculated to be > or = 0.01 microT.