Rh-POP Pincer Xantphos Complexes for C-S and C-H Activation. Implications for Carbothiolation Catalysis

The neutral Rh­(I)–Xantphos complex [Rh­(κ³-_P,O,P-Xantphos)­Cl]_<i>n</i>, <b>4</b>, and cationic Rh­(III) [Rh­(κ³-_P,O,P-Xantphos)­(H)₂]­[BAr^F₄], <b>2a</b>, and [Rh­(κ³-_P,O,P-Xantphos-3,5-C₆H₃(CF₃)₂)­(H)₂]­[BAr^F₄], <b>2b</b>, are described [Ar^F = 3,5-(CF₃)₂C₆H₃; Xantphos = 4,5-bis­(diphenylphosphino)-9,9-dimethylxanthene; Xantphos-3,5-C₆H₃(CF₃)₂ = 9,9-dimethylxanthene-4,5-bis­(bis­(3,5-bis­(trifluoromethyl)­phenyl)­phosphine]. A solid-state structure of <b>2b</b> isolated from C₆H₅Cl solution shows a κ¹-chlorobenzene adduct, [Rh­(κ³-_P,O,P-Xantphos-3,5-C₆H₃(CF₃)₂)­(H)₂(κ¹-ClC₆H₅)]­[BAr^F₄], <b>3</b>. Addition of H₂ to <b>4</b> affords, crystallographically characterized, [Rh­(κ³-_P,O,P-Xantphos)­(H)₂Cl], <b>5</b>. Addition of diphenyl acetylene to <b>2a</b> results in the formation of the C–H activated metallacyclopentadiene [Rh­(κ³-_P,O,P-Xantphos)­(ClCH₂Cl)­(σ,σ-(C₆H₄)­C­(H)CPh)]­[BAr^F₄], <b>7</b>, a rare example of a crystallographically characterized Rh–dichloromethane complex, alongside the Rh­(I) complex <i>mer</i>-[Rh­(κ³-_P,O,P-Xantphos)­(η²-PhCCPh)]­[BAr^F₄], <b>6</b>. Halide abstraction from [Rh­(κ³-_P,O,P-Xantphos)­Cl]_<i>n</i> in the presence of diphenylacetylene affords <b>6</b> as the only product, which in the solid state shows that the alkyne binds perpendicular to the κ³-POP Xantphos ligand plane. This complex acts as a latent source of the [Rh­(κ³-_P,O,P-Xantphos)]⁺ fragment and facilitates <i>ortho</i>-directed C–S activation in a number of 2-arylsulfides to give <i>mer</i>-[Rh­(κ³-_P,O,P-Xantphos)­(σ,κ¹-Ar)­(SMe)]­[BAr^F₄] (Ar = C₆H₄COMe, <b>8</b>; C₆H₄(CO)­OMe, <b>9</b>; C₆H₄NO₂, <b>10</b>; C₆H₄CNCH₂CH₂O, <b>11</b>; C₆H₄C₅H₄N, <b>12</b>). Similar C–S bond cleavage is observed with allyl sulfide, to give <i>fac</i>-[Rh­(κ³-_P,O,P-Xantphos)­(η³-C₃H₅)­(SPh)]­[BAr^F₄], <b>13</b>. These products of C–S activation have been crystallographically characterized. For <b>8</b> in situ monitoring of the reaction by NMR spectroscopy reveals the initial formation of <i>fac</i>-κ³-<b>8</b>, which then proceeds to isomerize to the <i>mer</i>-isomer. With the <i>para</i>-ketone aryl sulfide, 4-SMeC ₆H₄COMe, C–H activation <i>ortho</i> to the ketone occurs to give <i>mer</i>-[Rh­(κ³-_P,O,P-Xantphos)­(σ,κ¹-4-(COMe)­C₆H₃SMe)­(H)]­[BAr^F₄], <b>14</b>. The temporal evolution of carbothiolation catalysis using <i>mer</i>-κ³-<b>8</b>, and phenyl acetylene and 2-(methylthio)­acetophenone substrates shows initial fast catalysis and then a considerably slower evolution of the product. We suggest that the initially formed <i>fac</i>-isomer of the C–S activation product is considerably more active than the <i>mer</i>-isomer (i.e., <i>mer</i>-<b>8</b>), the latter of which is formed rapidly by isomerization, and this accounts for the observed difference in rates. A likely mechanism is proposed based upon these data

Correlation between mass transfer coefficient kLa and relevant operating parameters in cylindrical disposable shaken bioreactors on a bench-to-pilot scale

Background: Among disposable bioreactor systems, cylindrical orbitally shaken bioreactors show important advantages. They provide a well-defined hydrodynamic flow combined with excellent mixing and oxygen transfer for mammalian and plant cell cultivations. Since there is no known universal correlation between the volumetric mass transfer coefficient for oxygen kLa and relevant operating parameters in such bioreactor systems, the aim of this current study is to experimentally determine a universal kLa correlation.Results: A Respiration Activity Monitoring System (RAMOS) was used to measure kLa values in cylindrical disposable shaken bioreactors and Buckingham's -Theorem was applied to define a dimensionless equation for kLa. In this way, a scale- and volume-independent kLa correlation was developed and validated in bioreactors with volumes from 2 L to 200 L. The final correlation was used to calculate cultivation parameters at different scales to allow a sufficient oxyge n supply of tobacco BY-2 cell suspension cultures.Conclusion: The resulting equation can be universally applied to calculate the mass transfer coefficient for any of seven relevant cultivation parameters such as the reactor diameter, the shaking frequency, the filling volume, the viscosity, the oxygen diffusion coefficient, the gravitational acceleration or the shaking diameter within an accuracy range of +/- 30%. To our knowledge, this is the first kLa correlation that has been defined and validated for the cited bioreactor system on a bench-to-pilot scale

Photocatalytic Degradation of Methylene Blue Dye from Wastewater by Using Doped Zinc Oxide Nanoparticles

ZnO is a semiconductor material that has important physical and chemical properties, which are frequently and significantly enhanced by the addition of impurities, such as doping. A study of the structural properties of pristine and functionalized (i.e., doped with Antimony and Tungsten) ZnO nanoparticles has been conducted for the photocatalyst-based degradation of methylene blue (MB) dye under both Ultraviolet (UV) and solar light. Authors have used a 1% concentration of dopant for doping purposes. The synthesized materials were characterized for structural analysis, functional group identification, spectroscopic measurements, and morphological examination using X-ray diffraction (XRD), Fourier transform-infrared (FTIR), UV-Vis spectroscopy (UV-Vis), and Field emission scanning electron microscope (FESEM) techniques. XRD analysis confirmed that the synthesized-doped materials retained the wurtzite hexagonal structure with a purity of 99%. Transmission electron microscope (TEM) analysis data reveals the average size of pure ZnO-NPs was found to be 7 nm; after doping the size was found to be increased to 18 nm and 9.55 nm, respectively, for ZnO-W and ZnO-Sb. As per FESEM analysis results, minor morphological changes were observed after doping. The Ultraviolet Differential reflectance spectroscopy UV-DRS study revealed the confirmation of ZnO doping with antimony and tungsten, which exhibited a blue shift. The decrease in the band-gap on doping makes the ZnO-NPs more efficient for photocatalytic applications. The photocatalytic efficiency of pristine and doped ZnO-NPs catalysts for methylene blue photocatalytic degradation (PCD) was analyzed under both UV and solar irradiation. This study analyzed the effect of pH, nano-photocatalyst dose, and initial dye concentration (ICD) on the PCD of MB. The obtained analytical results showed that the ideal conditions for the PCD of MB dye are as follows: pH = 9, the quantity of the nano-photocatalyst used was 300 mg/L, and an initial MB dye dose of 10 ppm. These conditions lead to a PCD of about 91% of the MB dye by using ZnO-Sb nano-photocatalyst on exposure to solar radiation. The reusability study also revealed the stability of nano-photocatalysts. The current research may pave the way for the removal of hazardous dyes from wastewater discharged by many industries

Size-quantization in extremely small CdS clusters formed in calixarene LB films

CdS nanoparticles have been formed within Y-type Langmuir-Blodgett (LB) films of cadmium salts of calix(8)- and calix(4)-arene by reaction with H2S. UV-vis absorption spectra of the LB films, measured at room temperature, show well-resolved transitions between size-quantization levels in CdS clusters. The size of the CdS particles, obtained by Gaussian fitting of the experimental spectra, is 1.5 +/- 0.3 nm, which is much less than those reported for fatty acid LB films. The particle size does net depend either on the type of calixarene or the number of LB layers. LB films were also characterised by X-ray diffraction and ellipsometry which show the film thickness do not change substantially after treatment with H2S. The mechanism of CdS nanoparticles formation is discussed. (C) 1998 Published by Elsevier Science S.A. All rights reserved

Receptor-defined subtypes of breast cancer in indigenous populations in Africa: a systematic review and meta-analysis.

BACKGROUND: Breast cancer is the most common female cancer in Africa. Receptor-defined subtypes are a major determinant of treatment options and disease outcomes but there is considerable uncertainty regarding the frequency of poor prognosis estrogen receptor (ER) negative subtypes in Africa. We systematically reviewed publications reporting on the frequency of breast cancer receptor-defined subtypes in indigenous populations in Africa. METHODS AND FINDINGS: Medline, Embase, and Global Health were searched for studies published between 1st January 1980 and 15th April 2014. Reported proportions of ER positive (ER+), progesterone receptor positive (PR+), and human epidermal growth factor receptor-2 positive (HER2+) disease were extracted and 95% CI calculated. Random effects meta-analyses were used to pool estimates. Fifty-four studies from North Africa (n=12,284 women with breast cancer) and 26 from sub-Saharan Africa (n=4,737) were eligible. There was marked between-study heterogeneity in the ER+ estimates in both regions (I2>90%), with the majority reporting proportions between 0.40 and 0.80 in North Africa and between 0.20 and 0.70 in sub-Saharan Africa. Similarly, large between-study heterogeneity was observed for PR+ and HER2+ estimates (I2>80%, in all instances). Meta-regression analyses showed that the proportion of ER+ disease was 10% (4%-17%) lower for studies based on archived tumor blocks rather than prospectively collected specimens, and 9% (2%-17%) lower for those with ≥ 40% versus those with <40% grade 3 tumors. For prospectively collected samples, the pooled proportions for ER+ and triple negative tumors were 0.59 (0.56-0.62) and 0.21 (0.17-0.25), respectively, regardless of region. Limitations of the study include the lack of standardized procedures across the various studies; the low methodological quality of many studies in terms of the representativeness of their case series and the quality of the procedures for collection, fixation, and receptor testing; and the possibility that women with breast cancer may have contributed to more than one study. CONCLUSIONS: The published data from the more appropriate prospectively measured specimens are consistent with the majority of breast cancers in Africa being ER+. As no single subtype dominates in the continent availability of receptor testing should be a priority, especially for young women with early stage disease where appropriate receptor-specific treatment modalities offer the greatest potential for reducing years of life lost. Please see later in the article for the Editors' Summary

Deleterious Effect of Air Pollution on Human Microbial Community and Bacterial Flora: A Short Review

A balanced microbiota composition is requisite for normal physiological functions of the human body. However, several environmental factors such as air pollutants may perturb the human microbiota composition. It is noticeable that currently around 99% of the world’s population is breathing polluted air. Air pollution’s debilitating health impacts have been studied scrupulously, including in the human gut microbiota. Nevertheless, air pollution’s impact on other microbiotas of the human body is less understood so far. In the present review, the authors have summarized and discussed recent studies’ outcomes related to air pollution-driven microbiotas’ dysbiosis (including oral, nasal, respiratory, gut, skin, and thyroid microbiotas) and its potential multi-organ health risks