Catalytic and inhibitory effects of dissolved Cd2+ on C3H8 electro-oxidation

Studies have been made of the effect of Cd²⁺ on the oxidation rate of C₃H₈ in 80% H₃PO₄ at 130 C on platinized Pt electrodes.Dissolved Cd²⁺ discharges, probably as Cd⁰, and forms a stable sub-monolayer on a Pt electrode at potentials as high as 0·5 V versus RHE. Although this Cd⁰ layer is apparently substantially desorbed in favor of adsorbed hydrocarbon, C₃H₈ adsorption is inhibited in its presence. C₃H₈ oxidation is also inhibited. However, the C₃H₈ oxidation rate is observed to increase under some circumstances, and this appears to be because Cd isabsorbed into the Pt lattice. Co-plating of Cd and Pt leads to an electrode which, once the excess Cd has been removed, appears to be stable, and which catalyses C₃H₈ oxidation by about a factor of three at 0·25 V. Above 0·3 V, this absorbed Cd somewhat inhibits C₃H₈ oxidation.     

Polymer on Top: Current Limits and Future Perspectives of Quantitatively Evaluating Surface Grafting

Well‐defined polymer strands covalently tethered onto solid substrates determine the properties of the resulting functional interface. Herein, the current approaches to determine quantitative grafting densities are assessed. Based on a brief introduction into the key theories describing polymer brush regimes, a user's guide is provided to estimating maximum chain coverage and—importantly—examine the most frequently employed approaches for determining grafting densities, i.e., dry thickness measurements, gravimetric assessment, and swelling experiments. An estimation of the reliability of these determination methods is provided via carefully evaluating their assumptions and assessing the stability of the underpinning equations. A practical access guide for comparatively and quantitatively evaluating the reliability of a given approach is thus provided, enabling the field to critically judge experimentally determined grafting densities and to avoid the reporting of grafting densities that fall outside the physically realistic parameter space. The assessment is concluded with a perspective on the development of advanced approaches for determination of grafting density, in particular, on single‐chain methodologies.     

Precisely Controlled Microsphere Design via Visible‐Light Cross‐Linking of Functional Prepolymers

A new strategy for particle synthesis is enabled by utilizing modern synthetic, polymer, and photochemical techniques to facilitate the synthesis of highly narrow–disperse multifunctional microspheres from visible‐light induced crosslinking of prepolymers in both a single and dual polymer system. The approach requires no stabilizers, bases, or initiators, and proceeds at ambient temperature to yield microspheres with a tunable size range (0.25–5 µm) in less than 4 h, depending largely on solvent composition, but also polymer concentration (2–10 mg mL^?1), ratio, and irradiation intensity (3–20 W). Critically, the visible‐light induced dimerization reaction exploited herein enables simple functional particle syntheses via a single polymer system. Underpinned by an in‐depth kinetic analysis of the particle formation as well as a detailed small molecule study, the mechanism for particle formation is also elucidated. Importantly, inherent advantages of the system are exploited for surface functionalization of residual acrylate and hydroxyl groups (generating inherently fluorescent particles).     

Analysis of microRNAs in Exosomes of Breast Cancer Patients in Search of Molecular Prognostic Factors in Brain Metastases

Brain metastases are the most severe tumorous spread during breast cancer disease. They are associated with a limited quality of life and a very poor overall survival. A subtype of extracellular vesicles, exosomes, are sequestered by all kinds of cells, including tumor cells, and play a role in cell-cell communication. Exosomes contain, among others, microRNAs (miRs). Exosomes can be taken up by other cells in the body, and their active molecules can affect the cellular process in target cells. Tumor-secreted exosomes can affect the integrity of the blood-brain barrier (BBB) and have an impact on brain metastases forming. Serum samples from healthy donors, breast cancer patients with primary tumors, or with brain, bone, or visceral metastases were used to isolate exosomes and exosomal miRs. Exosomes expressed exosomal markers CD63 and CD9, and their amount did not vary significantly between groups, as shown by Western blot and ELISA. The selected 48 miRs were detected using real-time PCR. Area under the receiver-operating characteristic curve (AUC) was used to evaluate the diagnostic accuracy. We identified two miRs with the potential to serve as prognostic markers for brain metastases. Hsa-miR-576-3p was significantly upregulated, and hsa-miR-130a-3p was significantly downregulated in exosomes from breast cancer patients with cerebral metastases with AUC: 0.705 and 0.699, respectively. Furthermore, correlation of miR levels with tumor markers revealed that hsa-miR-340-5p levels were significantly correlated with the percentage of Ki67-positive tumor cells, while hsa-miR-342-3p levels were inversely correlated with tumor staging. Analysis of the expression levels of miRs in serum exosomes from breast cancer patients has the potential to identify new, non-invasive, blood-borne prognostic molecular markers to predict the potential for brain metastasis in breast cancer. Additional functional analyzes and careful validation of the identified markers are required before their potential future diagnostic use.     

Out of the Closet: The Importance of Stories and Storytelling in Planning Practice

This article argues that story has a special importance in planning that has neither been fully understood nor sufficiently valued. Planning is performed through story, in a myriad of ways. The aim here is to unpack the many ways we use story: in policy, in process, in pedagogy, in critique, as a foundation, and as a catalyst for change. A better understanding of the work that stories do can make us better planners in at least three ways: by expanding our practical tools, by sharpening our critical judgment and by widening the circle of democratic discourse.     

Cattle, crops and clearing: Regional drivers of landscape change in the Brigalow Belt, Queensland, Australia, 1840–2004

Landscape change occurs through the interaction of a multitude of natural and human driving forces at a range of organisational levels, with humans playing an increasingly dominant role in many regions of the world. Building on the current knowledge of the underlying drivers of landscape change, a conceptual framework of regional landscape change was developed which integrated population, economic and cultural values, policy and science/technology. Using the Southern Brigalow Belt biogeographic region of Queensland as a case study, the role of natural and human drivers in landscape change was investigated in four phases of settlement since 1840. The Brigalow Belt has experienced comparable rates of vegetation clearance over the past 50 years to areas of tropical deforestation. Economic factors were important during all phases of development, but the five regional drivers often acted in synergy. Environmental constraints played a significant role in slowing rates of change. Temporal trends of deforestation followed a sigmoidal curve, with initial slow change accelerating though the middle phases then slowing in recent times. Future landscape management needs to take account of the influence of all the components of the conceptual framework, at a range of organisational levels, if more ecologically sustainable outcomes are to be achieved.     

Molecular basis of the constitutive activity and STI571 resistance of Asp816Val mutant KIT receptor tyrosine kinase

The receptor tyrosine kinase, KIT, displays activating mutations in the kinase domain, which are associated with various cancers. We have used homology modelling based on the crystal structures of the insulin receptor kinase in active and inactive conformations to predict the corresponding structures of the KIT kinase domain. We have prepared four KIT models, one each for the active and inactive conformations of the wild-type and of the Asp816Val mutant proteins. We have also placed ATP into the active conformations and the inhibitor, STI571, into the inactive conformations. All models have been fully energy minimised. The molecular modelling studies described here explain (i) why Asp816Val KIT is constitutively active, (ii) why the nature of the substituting amino acid at residue 816 is relatively unimportant, and (iii) why the Asp816Val substitution confers resistance to the KIT-inhibitory drug STI571. The models will be valuable for predicting other kinase inhibitory drugs that may be active on wild-type and mutant forms of KIT. During the course of this work, a crystal structure of the active conformation of the KIT kinase domain has been published. Our model of the active conformation of the Asp816Val mutant is strikingly similar to this crystal structure, whereas our model of the active conformation of the wild-type kinase domain of KIT differs from the crystal structure in some respects. The reasons for this apparent discrepancy are discussed.     

Immunological Properties of Inulin-Type Fructans

Beneficial effects of inulin-type fructans are discussed in view of studies that applied the oligosaccharides in colon cancer, chronic inflammatory diseases, vaccination efficacy, and prevention of infection and allergy. In the present paper, we discuss their immunomodulating effects. It is suggested that immunomodulation is elicited through indirect and direct mechanisms. Indirect mechanisms encompass stimulation of growth and activity of lactic acid bacteria, but can also be caused by fermentation products of these bacteria, i.e., short chain fatty acids. Evidence for direct effects on the immune system generally remains to be confirmed. It is suggested that inulin-type fructans can be detected by gut dendritic cells (DCs), through receptor ligation of pathogen recognition receptors (PRRs) such as Toll-like receptors, nucleotide oligomerization domain containing proteins (NODs), C-type lectin receptors, and galectins, eventually inducing pro- and anti-inflammatory cytokines. DCs may also exert antigen presenting capacity toward effector cells, such as B cells, T cells, and natural killer cells locally, or in the spleen. Inulin-type fructans may also ligate PRRs expressed on gut epithelium, which could influence its barrier function. Inulin-type fructans are potent immunomodulating food components that hold many promises for prevention of disease. However, more studies into the mechanisms, dose-effect relations, and structure-function studies are required.     

Formulation of a Biodegradable Detergent for Cleaning Oily Residues Generated during Industrial Processes

The use of toxic petroleum-based heavy oils is common in industrial processes. The cleaning of machines, equipment, and other surface covered in these oils is achieved with expensive products that are often also toxic and harmful to both the health of workers and the environment. The present paper proposes the development of a sustainable biodetergent made from plant-based materials. Tests were performed to determine the properties of the biodetergent in terms of its surfactant and emulsifying capacities, stability, toxicity, and the removal of heavy oil from glass plates and metallic surfaces. The formulation was composed of a natural solvent (cottonseed oil), a plant-based surfactant agent (saponin), and two natural stabilizers (carboxymethylcellulose and glycerine). The formulation was stable, nontoxic, and highly efficient, removing 100% of the heavy oil from glass and metallic surfaces. This solution developed in this study could be used in diverse industries with the need to clean machines and parts encrusted with oil and grease as well as the cleaning of floors covered with petroleum-based residues. A preliminary analysis of the economic feasibility of using the detergent was carried out at a Brazilian power plant. Besides the reduction in environmental impact due to the use of a nontoxic, biodegradable product as well as the reduction in health risks to workers associated with toxic cleaning products, this new product can have a considerable impact on the market as an environmentally friendly solution.