Synthesis and properties of novel bis(1,3-benzodithiolium)-type dications containing a biaryl unit: New redox systems undergoing reversible structural changes by electron transfer

In order to develop new redox systems which undergo reversible structural changes by electron transfer, bis(1,3-benzodithiolium)-type dications (5 21) containing a biaryl unit have been synthesized by hydride abstraction of the corresponding bis(1,3-benzodithiol-2-yl)biaryis (8). Reduction of 5 2, with zinc gave the corresponding intramolecular cyclization products (6), which reverted to 5(2+) by oxidation. Cyclic voltammetry also showed the efficient interconversion between both states. X-Ray analyses revealed that the twist angle of the biaryl unit decreases largely by reductive intramolecular cyclization.ArticleHETEROCYCLES. 69(1): 365 (2006)journal articl

Systematic Study of Short Range Antiferromagnetic Order and The Spin-Glass State in Lightly Doped La2-xSrxCuO4

Systematic measurements of the magnetic susceptibility were performed on single crystals of lightly doped La2-xSrxCuO4 (x=0.03, 0.04 and 0.05). For all samples the temperature dependence of the in-plane magnetic susceptibility shows typical spin-glass features with spin-glass transition temperatures Tg of 6.3K, 5.5K and 5.0K for x=0.03, 0.04 and 0.05, respectively. The canonical spin-glass order parameter extracted from the in-plane susceptibility of all the samples follows a universal scaling curve. On the other hand, the out-of-plane magnetic susceptibility deviates from Curie law below a temperature Tdv, higher than Tg. Comparing with previous neutron scattering results with an instrumental energy resolution of 0.25 meV from Wakimoto et al., the x-dependence of Tdv is qualitatively the same as that of Tel, the temperature below which the elastic magnetic scattering develops around (pi, pi). Thus, a revised magnetic phase diagram in the lightly doped region of La2-xSrxCuO4 is proposed. The Curie constants calculated from the in-plane susceptibility are independent of the Sr concentration. On the basis of the cluster spin-glass model, this fact might reflect an inhomogeneous distribution of doped holes in the CuO2 plane, such as in a stripe structure.Comment: 7 pages, 6 figure

Observation of New Incommensurate Magnetic Correlations at the Lower Critical Concentration for Superconductivity (x=0.05) in La(2-x)Sr(x)CuO4

Neutron-scattering experiments have been performed on lightly-doped La(2-x)Sr(x)CuO4 single crystals in both the insulating (x=0.03,0.04,0.05) and superconducting (x=0.06) regions. Elastic magnetic peaks are observed at low temperatures in all samples with the maximum peak linewidth occuring at the critical concentration x_c=0.05. New incommensurate peaks are observed only at x=0.05, the positions of which are rotated by 45 degrees in reciprocal space about (pi,pi) from those observed for x>=0.06 in the superconducting phase.Comment: 5 pages, LaTeX, 4 figures include

Self-reported non-adherence to P2Y12 inhibitors in patients undergoing percutaneous coronary intervention: Application of the medication non-adherence academic research consortium classification.

AIMS The Non-adherence Academic Research Consortium (NARC) has recently developed a consensus-based standardized classification for medication non-adherence in cardiovascular clinical trials. We aimed to assess the prevalence of NARC-defined self-reported non-adherence to P2Y12 inhibitors and its impact on clinical outcomes in patients undergoing percutaneous coronary intervention (PCI). METHODS AND RESULTS Using a standardized questionnaire administered at 1 year after PCI, we assessed the 4 NARC-defined non-adherence levels including type, decision-maker, reasons, and timing within the Bern PCI registry. The primary endpoint was the patient-oriented composite endpoint (POCE) defined as a composite of death, myocardial infarction, stroke, and any revascularization at 1 year. The recommended P2Y12 inhibitor duration was 12 months. Among 3,896 patients, P2Y12 inhibitor non-adherence was observed in 647 (17%) patients. Discontinuation was permanent in the majority of patients (84%). The decision was mainly driven by a physician (94%), and rarely by patients (6%). The most frequent reason was risk profile change (43%), followed by unlisted reasons (25%), surgery (17%), and adverse events (14%). Non-adherence occurred early (180 days) in 33%. The majority of POCE events (n = 421/502, 84%) occurred during adherence to the prescribed P2Y12 inhibitor. Permanent discontinuation, doctor-driven non-adherence, and risk profile change emerged as independent predictors for POCE. CONCLUSIONS In real-world PCI population treated with 1-year DAPT, non-adherence was observed in nearly one-fifth of patients. Non-adherence to P2Y12 inhibitors was associated with worse clinical outcomes, while the risk was related to underlying contexts. CLINICALTRIALS.GOV IDENTIFIER NCT02241291

The GATA1s isoform is normally down-regulated during terminal haematopoietic differentiation and over-expression leads to failure to repress MYB, CCND2 and SKI during erythroid differentiation of K562 cells

Background: Although GATA1 is one of the most extensively studied haematopoietic transcription factors little is currently known about the physiological functions of its naturally occurring isoforms GATA1s and GATA1FL in humans—particularly whether the isoforms have distinct roles in different lineages and whether they have non-redundant roles in haematopoietic differentiation. As well as being of general interest to understanding of haematopoiesis, GATA1 isoform biology is important for children with Down syndrome associated acute megakaryoblastic leukaemia (DS-AMKL) where GATA1FL mutations are an essential driver for disease pathogenesis. <p/>Methods: Human primary cells and cell lines were analyzed using GATA1 isoform specific PCR. K562 cells expressing GATA1s or GATA1FL transgenes were used to model the effects of the two isoforms on in vitro haematopoietic differentiation. <p/>Results: We found no evidence for lineage specific use of GATA1 isoforms; however GATA1s transcripts, but not GATA1FL transcripts, are down-regulated during in vitro induction of terminal megakaryocytic and erythroid differentiation in the cell line K562. In addition, transgenic K562-GATA1s and K562-GATA1FL cells have distinct gene expression profiles both in steady state and during terminal erythroid differentiation, with GATA1s expression characterised by lack of repression of MYB, CCND2 and SKI. <p/>Conclusions: These findings support the theory that the GATA1s isoform plays a role in the maintenance of proliferative multipotent megakaryocyte-erythroid precursor cells and must be down-regulated prior to terminal differentiation. In addition our data suggest that SKI may be a potential therapeutic target for the treatment of children with DS-AMKL

Wettability characteristics of an Al2O3/SiO2-based ceramic modified with CO2, Nd:YAG, excimer and high-power diode lasers

Interaction of CO2, Nd:YAG, excimer and high power diode laser (HPDL) radiation with the surface of an Al2O3/SiO2 based ceramic was found to effect significant changes in the wettability characteristics of the material. It was observed that interaction with CO2, Nd:YAG and HPDL radiation reduced the enamel contact angle from 1180 to 310, 340 and 330 respectively. In contrast, interaction with excimer laser radiation resulted an increase in the contact angle to 1210. Such changes were identified as being due to: (i) the melting and partial vitrification of the Al2O3/SiO2 based ceramic surface as a result of interaction with CO2, Nd:YAG HPDL radiation. (ii) the surface roughness of the Al2O3/SiO2 based ceramic increasing after interaction with excimer laser radiation. (iii) the surface oxygen content of the Al2O3/SiO2 based ceramic increasing after interaction with CO2, Nd:YAG and HPDL radiation. The work has shown that the wettability characteristics of the Al2O3/SiO2 based ceramic could be controlled and/or modified with laser surface treatment. In particular, whether the laser radiation had the propensity to cause surface melting. However, a wavelength dependance of the change of the wetting properties could not be deduced from the findings of this work

Magnetoresistance of antidot lattices with grain boundaries

The magnetotransport properties of antidot lattices containing artificially designed grain boundaries have been measured. We find that the grain boundaries broaden the commensurability resonances and displace them anisotropically. These phenomena are unexpectedly weak but differ characteristically from isotropic, Gaussian disorder in the antidot positions. The observations are interpreted in terms of semiclassical trajectories which tend to localize along the grain boundaries within certain magnetic field intervals. Furthermore, our results indicate how the transport through superlattices generated by self-organizing templates may get influenced by grain boundaries.Comment: 6 pages, 3 figure

Arterial oxygen content is precisely maintained by graded erythrocytotic responses in settings of high/normal serum iron levels, and predicts exercise capacity: an observational study of hypoxaemic patients with pulmonary arteriovenous malformations.

Oxygen, haemoglobin and cardiac output are integrated components of oxygen transport: each gram of haemoglobin transports 1.34 mls of oxygen in the blood. Low arterial partial pressure of oxygen (PaO2), and haemoglobin saturation (SaO2), are the indices used in clinical assessments, and usually result from low inspired oxygen concentrations, or alveolar/airways disease. Our objective was to examine low blood oxygen/haemoglobin relationships in chronically compensated states without concurrent hypoxic pulmonary vasoreactivity.165 consecutive unselected patients with pulmonary arteriovenous malformations were studied, in 98 cases, pre/post embolisation treatment. 159 (96%) had hereditary haemorrhagic telangiectasia. Arterial oxygen content was calculated by SaO2 x haemoglobin x 1.34/100.There was wide variation in SaO2 on air (78.5-99, median 95)% but due to secondary erythrocytosis and resultant polycythaemia, SaO2 explained only 0.1% of the variance in arterial oxygen content per unit blood volume. Secondary erythrocytosis was achievable with low iron stores, but only if serum iron was high-normal: Low serum iron levels were associated with reduced haemoglobin per erythrocyte, and overall arterial oxygen content was lower in iron deficient patients (median 16.0 [IQR 14.9, 17.4]mls/dL compared to 18.8 [IQR 17.4, 20.1]mls/dL, p<0.0001). Exercise tolerance appeared unrelated to SaO2 but was significantly worse in patients with lower oxygen content (p<0.0001). A pre-defined athletic group had higher Hb:SaO2 and serum iron:ferritin ratios than non-athletes with normal exercise capacity. PAVM embolisation increased SaO2, but arterial oxygen content was precisely restored by a subsequent fall in haemoglobin: 86 (87.8%) patients reported no change in exercise tolerance at post-embolisation follow-up.Haemoglobin and oxygen measurements in isolation do not indicate the more physiologically relevant oxygen content per unit blood volume. This can be maintained for SaO2 ≥78.5%, and resets to the same arterial oxygen content after correction of hypoxaemia. Serum iron concentrations, not ferritin, seem to predict more successful polycythaemic responses