Cr-Hollandite: Breaking Tradition with Todorokite-type Manganese Oxides

The synthesis of a tunneled hollandite-type manganese oxide with interstitial and framework Cr3+ is described. This unique material is prepared from a layered buserite precursor under conditions previously believed to only yield todorokite-type manganese oxides with larger tunnels. The influence of Cr3+ in promoting the hollandite structure has been investigated by selectively placing the cation either in interstitial or framework sites. The use of framework Cr3+ in combination with other interstitial cations generates related hollandite and todorokite derivatives. Catalytic oxidation reactions with benzyl alcohol and carbon monoxide have also been examined

Liquid Phase Electrochemistry at Ultralow Temperatures

Fluid electrolyte solutions based on mixtures of butyronitrile (PrCN) and ethyl chloride (EtCl) with or as electrolyte freeze below −180°C and provide excellent media for cryogenic electrochemical experiments. A 1:2 mixture of PrCN and EtCl exhibits the best combination of freezing point and ionic conductivity for ultralow temperature electrochemistry. Diffusion coefficients for bis(pentamethylcyclopentadienyl) iron are measurable by potential step chronoamperometry down to −160°C using a conventionally sized electrode, but the resistivity of the solvent mixture is such that potential sweep voltammetry benefits from the use of microdisk (10 and 25 μm diam Pt) or microband (0.2 μm wide Au) electrodes. Voltammetry at a chemically modified electrode down to −170°C is presented for the case of thin films

Manganese Oxide Thin Films Prepared by Nonaqueous Sol-Gel Processing: Preferential Formation of Birnessite

High quality manganese oxide thin films with smooth surfaces and even thicknesses have been prepared with a nonaqueous sol–gel process involving reduction of tetraethylammonium permanganate in methanol. Spin-coated films have been cast onto soft glass, quartz, and Ni foil substrates, with two coats being applied for optimum crystallization. The addition of alkali metal cations as dopants results in exclusive formation of the layered birnessite phase. By contrast, analogous reactions in bulk sol–gel reactions yield birnessite, tunneled, and spinel phases depending on the dopant cation. XRD patterns confirm the formation of well-crystallized birnessite. SEM images of Li-, Na-, and K–birnessite reveal extremely smooth films having uniform thickness of less than 0.5 μm. Thin films of Rb– and Cs–birnessite have more fractured and uneven surfaces as a result of some precipitation during the sol–gel transformation. All films consist of densely packed particles of about 0.1 μm. When tetrabutylammonium permanganate is used instead of tetraethylammonium permanganate, the sol–gel reaction yields amorphous manganese oxide as the result of diluted Mn sites in the xerogel film. Bilayer films have been prepared by casting an overcoat of K–birnessite onto an Na–birnessite film. However, Auger depth profiling indicates considerable mixing between the adjacent layers

Synthesis of a new hollandite-type manganese oxide with framework and interstitial Cr(III)

Hollandite with Cr(III) in both tunnel and framework sites has been prepared hydrothermally from layered manganese oxide precursors

Factors predicting clinically significant fatigue in women following treatment for primary breast cancer

Cancer-related fatigue is common, complex, and distressing. It affects 70–100% of patients receiving chemotherapy and a significant number who have completed their treatments. We assessed a number of variables in women newly diagnosed with primary breast cancer (BrCa) to determine whether biological and/or functional measures are likely to be associated with the development of clinically significant fatigue (CSF). Two hundred twenty-three women participated in a study designed to document the impact of the diagnosis and treatment of primary breast cancer on function. Forty-four had complete data on all variables of interest at the time of confirmed diagnosis but prior to treatment (baseline) and ≥9 months post-diagnosis. Objective measures and descriptive variables included history, physical examination, limb volume, hemoglobin, white blood cell count, and glucose. Patient-reported outcomes included a verbal numerical rating of fatigue (0–10, a score of ≥4 was CSF), five subscales of the SF-36, Physical Activity Survey, and Sleep Questionnaire. At baseline, the entire cohort (n = 223) and the subset (n = 44) were not significantly different for demographic, biological, and self-reported data, except for younger age (p = 0.03) and ER+ (p = 0.01). Forty-five percent had body mass index (BMI) ≥ 25, 52% were post-menopause, and 52% received modified radical mastectomy, 39% lumpectomy, 52% chemotherapy, 68% radiation, and 86% hormonal therapy. Number of patients with CSF increased from 1 at baseline to 11 at ≥9 months of follow-up. CSF at ≥9 months significantly correlated with BMI ≥ 25, abnormal white blood cell count, and increase in limb volume and inversely correlated with vigorous activity and physical function (p < 0.05). Fatigue increases significantly following the treatment of BrCa. Predictors of CSF include high BMI and WBC count, increase in limb volume, and low level of physical activity. These are remediable

Meta-analysis of genome-wide association studies of HDL cholesterol response to statins

BACKGROUND: In addition to lowering low density lipoprotein cholesterol (LDL-C), statin therapy also raises high density lipoprotein cholesterol (HDL-C) levels. Inter-individual variation in HDL-C response to statins may be partially explained by genetic variation.METHODS AND RESULTS: We performed a meta-analysis of genome-wide association studies (GWAS) to identify variants with an effect on statin-induced high density lipoprotein cholesterol (HDL-C) changes. The 123 most promising signals with p&lt;1×10(-4) from the 16 769 statin-treated participants in the first analysis stage were followed up in an independent group of 10 951 statin-treated individuals, providing a total sample size of 27 720 individuals. The only associations of genome-wide significance (p&lt;5×10(-8)) were between minor alleles at the CETP locus and greater HDL-C response to statin treatment.CONCLUSIONS: Based on results from this study that included a relatively large sample size, we suggest that CETP may be the only detectable locus with common genetic variants that influence HDL-C response to statins substantially in individuals of European descent. Although CETP is known to be associated with HDL-C, we provide evidence that this pharmacogenetic effect is independent of its association with baseline HDL-C levels.</p

Pharmacogenetic meta-analysis of genome-wide association studies of LDL cholesterol response to statins

Statins effectively lower LDL cholesterol levels in large studies and the observed interindividual response variability may be partially explained by genetic variation. Here we perform a pharmacogenetic meta-analysis of genome-wide association studies (GWAS) in studies addressing the LDL cholesterol response to statins, including up to 18,596 statin-treated subjects. We validate the most promising signals in a further 22,318 statin recipients and identify two loci, SORT1/CELSR2/PSRC1 and SLCO1B1, not previously identified in GWAS. Moreover, we confirm the previously described associations with APOE and LPA. Our findings advance the understanding of the pharmacogenetic architecture of statin response