Ligand-bridged dinuclear carbonyl compounds of rutheniun and osmium

Includes abstract.Includes bibliographical references (leaves 26-29).Ligand-bridged dinuc1ear carbonyl compounds of ruthenium and osmium have been successfully prepared and characterised by various analytical and spectroscopic techniques. X-ray crystal structures have been determined for the osmium complexes [OS2(CO)4(p-02CCsH4FeCsHs)2L2] {L = PPh3 (102), py (103)}. Some of the complexes were then investigated for their catalytic activity in the oxidation of cyc10hexane and octane. In this work, hydrogen peroxide was used as an oxidant and acetonitrile as the solvent. A higher selectivity for the alcohol products over the ketones was observed. The average ratio of alcohols to ketones was found to be 4.56 and 1.76 for cyc10hexane and octane respectively. The complexes [OS2(CO)6(p-02CMeh] (4) [Ru(CO)2(p-02CMe)2]n (86), [Ru2( CO )4(p-02CMe )(p-dppm h] [PF 6] (117) and [Ru2( CO)4(p -( 02CMe h(MeCN)2] (118), were tested as homogeneous catalysts for the isomerisation of terminal alkenes. Complex 4 was inactive while the complex 118 gave a 100 % conversion. It is proposed that the catalysis proceeded via the displacement of one acetonitrile ligand from the metal centre providing a vacant site onto which the substrate coordinated. The redox behaviour of the four complexes [Ru2(CO)2(p-COh

Fabrication of type-I indium-based near-infrared emitting quantum dots for biological imaging applications

Doctor Scientiae - DScSemiconductor nanocrystals or quantum dots (QDs) are fluorescent nanometer-sized particles which have physical dimensions that are smaller than the excitonic Bohr radius, large surface area-to-volume ratios, broad absorption spectra and very large molar extinction coefficients. Biomedical applications of QDs are mainly based on II-VI QDs containing cadmium, such as CdSe/ZnS. These cadmium-based systems are associated with high toxicity due to cadmium. As a result, potential replacements of cadmium-based QDs in biological applications are needed. In this study, InP/ZnSe QDs were synthesized for the first time using a one-pot hot injection method. Furthermore, a growth-doping method was used for silver, cobalt and iron incorporation into the InP core. Water compatibility was achieved through ligand exchange with 3- mercaptopropionic acid. In vitro cytotoxicity and imaging/internalization of the as-prepared MP A-InP/ZnSe and MP A-capped CdTe/ZnS QDs were evaluated. InP/ZnSe QDs were successfully synthesized with ZnSe shell causing a 1.4 times reduction in trap-related emission

One-pot synthesis and characterization of InP/ZnSe semiconductor nanocrystals

We report on the one-pot synthesis of InP/ZnSe quantum dots (QDs) using a precursor-based colloidal synthesis in a noncoordinating solvent environment. The structural and optical studies were carried out on the as-prepared InPQDs. The quantum yield of the nanocrystals was recorded as 6% and a 1.4 times reduction in the ratio of trap-related emission to band edge emission was observed on ZnSe passivation of the InPQDs.Web of Scienc

Independent and combined effects of improved water, sanitation, and hygiene, and improved complementary feeding, on child stunting and anaemia in rural Zimbabwe: a cluster-randomised trial.

BACKGROUND: Child stunting reduces survival and impairs neurodevelopment. We tested the independent and combined effects of improved water, sanitation, and hygiene (WASH), and improved infant and young child feeding (IYCF) on stunting and anaemia in in Zimbabwe. METHODS: We did a cluster-randomised, community-based, 2 × 2 factorial trial in two rural districts in Zimbabwe. Clusters were defined as the catchment area of between one and four village health workers employed by the Zimbabwe Ministry of Health and Child Care. Women were eligible for inclusion if they permanently lived in clusters and were confirmed pregnant. Clusters were randomly assigned (1:1:1:1) to standard of care (52 clusters), IYCF (20 g of a small-quantity lipid-based nutrient supplement per day from age 6 to 18 months plus complementary feeding counselling; 53 clusters), WASH (construction of a ventilated improved pit latrine, provision of two handwashing stations, liquid soap, chlorine, and play space plus hygiene counselling; 53 clusters), or IYCF plus WASH (53 clusters). A constrained randomisation technique was used to achieve balance across the groups for 14 variables related to geography, demography, water access, and community-level sanitation coverage. Masking of participants and fieldworkers was not possible. The primary outcomes were infant length-for-age Z score and haemoglobin concentrations at 18 months of age among children born to mothers who were HIV negative during pregnancy. These outcomes were analysed in the intention-to-treat population. We estimated the effects of the interventions by comparing the two IYCF groups with the two non-IYCF groups and the two WASH groups with the two non-WASH groups, except for outcomes that had an important statistical interaction between the interventions. This trial is registered with ClinicalTrials.gov, number NCT01824940. FINDINGS: Between Nov 22, 2012, and March 27, 2015, 5280 pregnant women were enrolled from 211 clusters. 3686 children born to HIV-negative mothers were assessed at age 18 months (884 in the standard of care group from 52 clusters, 893 in the IYCF group from 53 clusters, 918 in the WASH group from 53 clusters, and 991 in the IYCF plus WASH group from 51 clusters). In the IYCF intervention groups, the mean length-for-age Z score was 0·16 (95% CI 0·08-0·23) higher and the mean haemoglobin concentration was 2·03 g/L (1·28-2·79) higher than those in the non-IYCF intervention groups. The IYCF intervention reduced the number of stunted children from 620 (35%) of 1792 to 514 (27%) of 1879, and the number of children with anaemia from 245 (13·9%) of 1759 to 193 (10·5%) of 1845. The WASH intervention had no effect on either primary outcome. Neither intervention reduced the prevalence of diarrhoea at 12 or 18 months. No trial-related serious adverse events, and only three trial-related adverse events, were reported. INTERPRETATION: Household-level elementary WASH interventions implemented in rural areas in low-income countries are unlikely to reduce stunting or anaemia and might not reduce diarrhoea. Implementation of these WASH interventions in combination with IYCF interventions is unlikely to reduce stunting or anaemia more than implementation of IYCF alone. FUNDING: Bill & Melinda Gates Foundation, UK Department for International Development, Wellcome Trust, Swiss Development Cooperation, UNICEF, and US National Institutes of Health.The SHINE trial is funded by the Bill & Melinda Gates Foundation (OPP1021542 and OPP113707); UK Department for International Development; Wellcome Trust, UK (093768/Z/10/Z, 108065/Z/15/Z and 203905/Z/16/Z); Swiss Agency for Development and Cooperation; US National Institutes of Health (2R01HD060338-06); and UNICEF (PCA-2017-0002)

pH control using two continuous stirred tank reactors in series

The control of pH is one of the most difficult chemical control schemes in industry. Often, large tanks are used to control pH. The pH in these large tanks frequently overshoots the desired pH set-point and usually takes a long time to reach the desired set-point. In this work, a conceptual pH control process was developed and tested by using two small continuous stirred tank reactors (CSTRs). In this two-step system, the bulk of the neutralization is carried out in the first reactor and then fine-tuned in the second reactor. The conceptual neutralization model was built by analyzing the chemistry behind pH. Because pH is a nonlinear function of hydrogen ion concentration (pH= -log [H+]), the hydrogen ion concentration was chosen as the process measured variable. The slope (Gain) was calculated from a titration curve obtained from a polynomial derived from neutralization chemistry and a practical titration. The process dynamics were then fitted into the classic proportional, integral, and differential (PID) controller using the Internal Model Control (IMC) tuning method. The robust tuning parameters produced by the IMC method were able to bring the pH in the first CSTR to the desired set-point. In addition, disturbances from vibrations produced by the pump and magnetic stirrer, slight variations in reactant concentration, and pH probe lags were easily eliminated. Most importantly, pH in the second CSTR settled on the desired neutral set-point of pH 7.0 after brief oscillations. The process was repeatable when the reactors where scaled up one hundred times using synthetic waste water. Autotune variation results produced similar process dynamics to those produced by calculating the slope from the titration curve

Indium Phosphide-Based Semiconductor Nanocrystals and Their Applications

Semiconductor nanocrystals or quantum dots (QDs) are nanometer-sized fluorescent materials with optical properties that can be fine-tuned by varying the core size or growing a shell around the core. They have recently found wide use in the biological field which has further enhanced their importance. This review focuses on the synthesis of indium phosphide (InP) colloidal semiconductor nanocrystals. The two synthetic techniques, namely, the hot-injection and heating-up methods are discussed. Different types of the InP-based QDs involving their use as core, core/shell, alloyed, and doped systems are reviewed. The use of inorganic shells for surface passivation is also highlighted. The paper is concluded by some highlights of the applications of these systems in biological studies

Phytochemical Fingerprinting and Activity of Extracts from the Leaves of Dolichos kilimandscharicus (Fabaceae) on Jurkat-T Cells

Plants are a source of over a quarter of the prescription drugs currently in use worldwide. Zimbabwe has a rich plant biodiversity with only a limited number reported for the treatment of cancer. The leaf extracts of Dolichos kilimandscharicus were selected for the screening of their antiproliferative efficacy and cytotoxicity effects. This plant has increasingly been used by local folk as a treatment for cancer or cancer-related symptoms though its bioactivity has not been scientifically determined. This investigation also sought to identify constituent compounds in the crude extract preparations responsible for their antiproliferative efficacy. The antiproliferative effects of six-leaf extracts on Jurkat-T in vitro were investigated using the Trypan blue exclusion assay. The extracts were tested with increasing concentration, using chlorambucil as a standard anticancer drug. Cytotoxicity of extracts was determined against RAW 264.7 cells using a colorimetric tetrazolium-based assay. In additionthe ability of the extracts to induce apoptosis was determined for the most potent leaf extracts. The order of potency of the leaf extracts of D. kilimandscharicus against Jurkat-T cell line was found to be MeOH < Ethyl Acetate < DCM: MeOH < EtOH with IC50s of 33.56, 30.44, 22.93, and 21.59 μg/mL, respectively. Furthermore, the most potent extracts exhibited very low cytotoxicity against all the tested cells. D. kilimandscharicus leaf extracts induced apoptosis in the Jurkat-T cells as was shown by DNA fragmentation. UPLC-MS analysis of crude extracts led to the identification of 23 compounds from the ethanol extract and these may be responsible for the observed antiproliferative effects. Rutin, quercetin, luteolin, apigenin, hispidulin, kaempferol derivatives, as well as caffeoylquinic acid are some of the compounds identified in the extracts. The results of this study showed that the ethanol and ethyl acetate leaf extracts of D. kilimandscharicus have antiproliferative activity against Jurkat-T cells and may act by inducing apoptosis.. The current findings offer supporting evidence for the use of these plant species in the treatment of cancer in ethnomedicinal practices

Selective isomerization of 1-alkenes by binary metal carbonyl compounds

An efficient and selective isomerization of 1-alkenes to their corresponding 2-alkenes is achieved by using binary metal carbonyls such as Ru-3(CO)(12) as catalysts. Possible mechanisms are discussed. Substituents on the 1-alkene have a significant effect on the isomerization. (C) 2008 Elsevier Ltd. All rights reserved