Optimized Synthesis and Structural Characterization of the Borosilicate MCM-70

A structure analysis of the borosilicate zeolite MCM-70, whose synthesis had been patented in 2003, was reported in 2005. Unfortunately, that structure analysis was somewhat ambiguous. Anisotropic line broadening made it difficult to model the peak shape, some peaks in the electron density map could not be interpreted satisfactorily, the framework geometry was distorted, and MAS NMR results were partially contradictory. In an attempt to resolve some of these points, an optimization of the synthesis was undertaken, and the structure was reinvestigated. The structure was solved from synchrotron powder diffraction data collected on an as-synthesized sample (Pmn2_1, a = 13.3167(1) Å, b = 4.6604(1) Å, c = 8.7000(1) Å) using a powder charge-flipping algorithm. The framework topology, with a 1-dimensional, 10-ring channel system, is identical to the one previously reported. However, the B in this new sample was found to be ordered in the framework, fully occupying one of the four tetrahedral sites. Two extra-framework K^+ ion positions, each coordinated to five framework O atoms and one water molecule, were also found. The solid state ^(29)Si, ^(11)B and ^1H NMR results are fully consistent with this ordered structure

Gas-Phase Complexes of Americium and Lanthanides with a Bis-triazinyl Pyridine: Reactivity and Bonding of Archetypes for F-Element Separations.

Bis-triazinyl pyridines (BTPs) exhibit solution selectivity for trivalent americium over lanthanides (Ln), the origins of which remain uncertain. Here, electrospray ionization was used to generate gas-phase complexes [ML3]3+, where M = La, Lu, or Am and L is EtBTP 2,6-bis(5,6-diethyl-1,2,4-triazin-3-yl)-pyridine. Collision-induced dissociation (CID) of [ML3]3+ in the presence of H2O yielded a protonated ligand [L(H)]+ and hydroxide [ML2(OH)]2+ or hydrate [ML(L-H)(H2O)]2+, where (L-H)- is a deprotonated ligand. Although solution affinities indicate stronger binding of BTPs toward Am3+ versus Ln3+, the observed CID process is contrastingly more facile for M = Am versus Ln. To understand the disparity, density functional theory was employed to compute potential energy surfaces for two possible CID processes, for M = La and Am. In accordance with the CID results, both the rate determining transition state barrier and the net energy are lower for [AmL3]3+ versus [LaL3]3+ and for both product isomers, [ML2(OH)]2+ and [ML(L-H)(H2O)]2+. More facile removal of a ligand from [AmL3]3+ by CID does not necessarily contradict stronger Am3+-L binding, as inferred from solution behavior. In particular, the formation of new bonds in the products can distort kinetics and thermodynamics expected for simple bond cleavage reactions. In addition to correctly predicting the seemingly anomalous CID behavior, the computational results indicate greater participation of Am 5f versus La 4f orbitals in metal-ligand bonding

Epigenetic and antitumor effects of platinum(IV)-octanoato conjugates

We present the anticancer properties of cis, cis, trans-[Pt(IV)(NH3)2Cl2(OA)2] [Pt(IV)diOA] (OA = octanoato), Pt(IV) derivative of cisplatin containing two OA units appended to the axial positions of a six-coordinate Pt(IV) center. Our results demonstrate that Pt(IV)diOA is a potent cytotoxic agent against many cancer cell lines (the IC50 values are approximately two orders of magnitude lower than those of clinically used cisplatin or Pt(IV) derivatives with biologically inactive axial ligands). Importantly, Pt(IV)diOA overcomes resistance to cisplatin, is significantly more potent than its branched Pt(IV) valproato isomer and exhibits promising in vivo antitumor activity. The potency of Pt(IV)diOA is a consequence of several factors including enhanced cellular accumulation correlating with enhanced DNA platination and cytotoxicity. Pt(IV)diOA induces DNA hypermethylation and reduces mitochondrial membrane potential in cancer cells at levels markedly lower than the IC50 value of free OA suggesting the synergistic action of platinum and OA moieties. Collectively, the remarkable antitumor effects of Pt(IV)diOA are a consequence of the enhanced cellular uptake which makes it possible to simultaneously accumulate high levels of both cisplatin and OA in cells. The simultaneous dual action of cisplatin and OA by different mechanisms in tumor cells may result in a markedly enhanced and unique antitumor effects of Pt(IV) prodrugs

Genetic exchange in <i>Trypanosoma brucei</i>: evidence for mating prior to metacyclic stage development

It is well established that genetic exchange occurs between Trypanosoma brucei parasites when two stocks are used to infect tsetse flies under laboratory conditions and a number of such crosses have been undertaken. Both cross and self-fertilisation can take place and, with the products of mating being the equivalent of F1 progeny in a Mendelian system and. Recently, analysis of a large collection of independent progeny using a series of polymorphic micro and minisatellite markers, has formally demonstrated that the allelic segregation at loci on each of the 11-megabase chromosomes conforms to ratios predicted for a classical diploid genetic system involving meiosis as well as independent assortment of markers on different chromosomes. Further extensive analysis of these F1 progeny, using a large panel of micro and minisatellite markers, has led to the construction of a genetic map of one parasite stock A. MacLeod, A. Tweedie and S. McLellan et al., The genetic map of Trypanosoma brucei, Nucleic Acids Res 33 (2005), pp. 6688–6693. Full Text via CrossRef | View Record in Scopus | Cited By in Scopus (10)

Assessing the effects of urban development and climate change on flooding in the Greater Port-Harcourt watershed, Niger Delta, Nigeria

Developing countries have been rapidly urbanising over the last decades, resulting in major environmental pressures and increased vulnerability to natural disasters. A complex combination of factors, including climate change, land use change, poorly implemented regulation and a lack of integrated planning has often resulted in environmental degradation and disproportionate impacts of natural disasters affecting millions worldwide, particularly in tropical cities. The main aim of this study is to understand the effects of land-use and climate change on flooding in the Greater Port-Harcourt watershed. The specific research objectives were: to understand the historical and future land use /land cover changes; to understand the magnitude of change in hydrologic and hydraulic conditions due to land-use and climate changes; to assess the influence of different forest mitigation scenarios on peak-discharge; and to make recommendations on how to improve future planning using insights from this study. Methodologically, the post-classification change detection method was applied to examine the extent and nature of historical LULC changes using remotely sensed data. Future LULC changes were estimated by superimposing the 2060 digitised Masterplan map on the year 2003 baseline imagery. Hydrologic changes were assessed using HEC-HMS model, while changes in the hydraulic condition were assessed using HEC-RAS model. Model output was further used to map flood hazards, flood zones and damage potential. Priority areas and infrastructure at risk were identified by means of their location in flood zones and exposure to floods with high damage potential. On the extent of change, this study revealed that urbanisation and loss of agricultural land had been the dominant and intensive land use change in the watershed. Urbanisation is projected to almost double its 2003 extent by 2060 and is likely to remain the dominant force of land use change. On the nature of change, this study found that urban land was the most dynamic in terms of gross gain and net change. It exhibited the grossest gain (about 9% of the watershed) and the grossest loss leading to a high net change of about 8.6%. In fact, the most prominent transition was the conversion of agricultural land (about 422km2) to urban land, and roughly 93.3% of all conversions to urban land resulted from agricultural land. On the process of change, urban land mainly experienced a net-type of change (change in quantity), whereas changes in agricultural land was more of a swap-type of change (change in location). Importantly, the study reveals that the impact on flood flow was historically significant (about 68%) and is projected to amplify in future, however, these changes are largely attributed to increased storm size. Urbanisation is likely to have little or no impact on annual maximum peak flow at the watershed scale; however, urbanisation is projected to have a considerable impact on peak flow in a number of subbasins, which could have severe implications for flash flooding in those subbasins. Similarly, afforestation could have little or no impact on future maximum peak flow when assessed at the watershed scale. Although some subbasins experienced changes in peak flow, the effect of forest is variable. The study concludes that although the impact of urbanisation is projected to be insignificant at the watershed scale, it could also increase flood risk due to increasing developments in floodplains and channel encroachment. Priority infrastructure and areas requiring urgent flood risk management include the Port-Harcourt seaports, Onne seaport, the University of Science and Technology and cement factory. Priority areas in the Masterplan are mainly in the south (Phase 3), comprising of the Air force base and the residential area near Onne seaport. Lastly, approximately 8.1km and 189m of road and rail network are at greater risk of flooding by means of their exposure to floods with the highest damage potential. Based on this study, I have furthered understanding by showing that the transition to urban land category was dominated by net changes (i.e. changes in quantity). I have also furthered understanding by showing that substantial changes in future urban land-use may not have significant effect on flood parameters. My main contribution to knowledge is that despite the high rate of urbanisation in the GPH watershed and its minimal impact on flooding (which could be due the large size of the storm and watershed), urbanisation could still increase flood risk due to greater exposure of elements at risk in the flood plains to damaging floods. Based on the results, the study recommends that the development authorities should integrate both structural measures (mainly for flood defence around existing developments) and non-structural measures (primarily for future developments). For flood risk management research, this study recommends that conclusions about the effects of urbanisation should not be made solely on the basis of changes in hydrology and river hydraulics, however researchers should also consider the exposure of important elements at risk within the floodplains under study to better understand the effects of urbanisation. Moreover, to better understand urbanisation effects on runoff dynamics in other watersheds, this study recommends that research efforts should be concerted in understanding subbasin-scale changes given that the effects of urbanisation are more pronounced in smaller basins

Prescribing competency assessment for Canadian medical students: a pilot evaluation

Background: The knowledge and ability to prescribe safely and effectively is a core competency for every graduating medical student. Our previous research suggested concerns about medical student prescribing abilities, and interest in a standardized assessment process. Methods: A multi-year cross-sectional study evaluating the feasibility, acceptability, and discriminative ability of an online prescribing competency assessment for final year Canadian medical students was conducted. Students at nine sites of four Ontario medical schools were invited to participate in an online one-hour exam of eight domains related to prescribing safely. Student feedback on perceived fairness, clarity, and ease of use formed the primary outcome. Exam performance and parity between schools were the secondary outcome.  Results: A total of 714 students completed the assessment during spring final review courses between 2016 and 2018. Student feedback was more favourable than not for appropriateness of content (53.5% agreement vs 18.3% disagreement), clarity of questions (65.5% agreement vs 11.6% disagreement), question layout and presentation (70.8% agreement vs 12.2% disagreement), and ease of use of online interface (67.1% agreement vs 13.6% disagreement). Few (23.6% believed their course work had prepared them for the assessment. Mean total exam score was 70.0% overall (SD 10.4%), with 47.6% scoring at or above the pass threshold of 70%. Conclusion: Our prescribing competency assessment proved feasible, acceptable, and discriminative, and indicated a need for better medical school training to improve prescribing competency. Further evaluation in a larger sample of medical schools is warranted

Oxoplatin‐Based Pt(IV) Lipoate Complexes and Their Biological Activity

α‐Lipoic acid, known for its anti‐inflammatory and antioxidant activity, represents a promising ligand for Pt(IV) prodrugs. Three new Pt(IV) lipoate complexes were synthesized and characterized by NMR spectroscopy ( 1 H, 13 C, 195 Pt), mass spectrometry and elemental analysis. Due to the low solubility of the complex containing two axial lipoate ligands, further experiments to examine the biological activity were performed with two Pt(IV) complexes containing just one axial lipoate ligand. Both complexes exhibit anticancer activity and produce reactive oxygen species (ROS) in the cell lines tested. Especially, the monosubstituted complex can be reduced by ascorbic acid and forms adducts with 9‐methylguanine (9MeG), which is favorable for the formation of DNA‐crosslinks in the cells

Transcriptomes of post-mitotic neurons identify the usage of alternative pathways during adult and embryonic neuronal differentiation

Original Panther analysis tool data tables showing values and p -values for overrepresentation data sets. (XLSX 21 kb

Nonlinear Properties of Chalcogenide Glass Fibers

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