Thermal Ageing Induced Effects on Pd/LaFeO3 for NOx Reduction by Hydrocarbons: Influence of the Preparation Method

The influence of the support synthesis for the preparation of supported Pd/LaFeO₃ perovskite based catalysts and the nature of the palladium precursor on the catalytic performances in the selective reduction of NO to N₂ by hydrocarbons have been investigated. According to the preparation method, subsequent surface and bulk characterisation revealed significant changes in the degree of dispersion and the chemical environment of oxidic palladium species depending on the extent of interaction with the support. Pd nitrate precursor leads to the stabilisation of the Pd surface concentration. The metal support interactions thus obtained strongly enhance the catalytic performances, particularly the resistance to thermal ageing whereas sol–gel synthesis produces the higher support activity.     

Synthesis, cytotoxicity, and COMPARE analysis of ferrocene and [3]ferrocenophane tetrasubstituted olefin derivatives against human cancer cells

Herein we report the antiproliferative effects of a series of 28 compounds against the MDA-MB-231 breast cancer cell line, including the synthesis of seven new [3]ferrocenophanyl and four new ferrocenyl compounds. For each p-R-phenyl substitution pattern investigated, the [3]ferrocenophanyl derivatives were more cytotoxic than the corresponding ferrocenyl derivative, with the highest activity found for compounds with protic substituents. Theoretical calculations of the HOMO-LUMO gap for the molecules in the Fe3(+) oxidation state suggest a higher reactivity for the [3]ferrocenophanyl derivatives. A lead compound from each series, a [3]ferrocenophanyl and a ferrocenyl compound, possessing two phenol groups, were screened against the NCI/DTP 60-cell-line panel. The mean activity over all cell lines was better than cisplatin for both compounds, and both compounds showed subpanel selectivity for leukemia, CNS cancer, and renal cancer. Low systemic toxicity and lack of interaction with DNA (when in the reduced form), suggest that the compounds may act as prodrugs.     

Surrogate endpoints for overall survival in advanced colorectal cancer: a clinician's perspective

Surrogate endpoints in oncology research and practice have garnered increasing attention over the past two decades. This activity has largely been driven by the promise surrogate endpoints appear to hold: the potential to get new therapies to seriously ill patients more rapidly. However, uncertainties abound. Even agreeing upon a definition of a "valid" surrogate endpoint has not been a straightforward exercise; this article begins by highlighting differences in how this term has been previously captured and applied, as well as laying out the basic criteria essential for its application in advanced colorectal cancer. Ideally, these elements include (but are not limited to) ease of measurement, rapid indication of treatment effect, and, most importantly, reliable and consistent prediction of the true impact of a treatment on the ultimate outcome of interest: overall survival. The strengths and weaknesses of current potential surrogate endpoints in advanced colorectal cancer, including performance status, carcinoembryonic antigen plasma level, overall response rate, time to progression, and disease-free survival, are each considered in turn. Finally, limitations of surrogate endpoints in the clinical setting, including challenges in extrapolation to new therapies, and the incomplete provision of information about potential adverse effects, are discussed. Work remains to be done between physicians and statisticians to bridge the gap between that which is statistically demonstrable and that which will be clinically useful.The term ;surrogate endpoint' was virtually unknown by most oncologists 15 years ago. A search in PubMed [http://www.ncbi.nlm.nih.gov] based on the words ;surrogate and cancer' shows that more than 2000 papers were published in medical journals in the last 20 years, with a dramatic increase of interest in the last five years. Interestingly, the same trend is observed when the words ;surrogate and heart' are entered into PubMed, suggesting that the issue of surrogate endpoints goes beyond the field of oncology, although the frequency of discussion varies (Figure 1; note different y-axis scales for oncology and cardiology).The goal of the present paper is to discuss the main issues surrounding surrogate endpoints from a clinician's point of view, using as an example surrogate endpoints of overall survival (OS) in advanced colorectal cancer (ACC).     

Generation of carrier peptides for the delivery of nucleic acid drugs in primary cells

Now that the human genome has been decoded, the demand for novel therapeutic concepts, such as gene and stem cell therapy, is higher than ever before. Although new and better pharmaceutical agents are available, their efficient delivery to the intracellular site of action is still a serious challenge. A possible solution to this problem is the use of cell-penetrating peptides as delivery vectors, including derivatives of human calcitonin (hCT). The aim of this study was to synthesise novel branched hCT-derived peptides for the noncovalent delivery of nucleic acids. The uptake of the resulting oligocationic peptides into various cell lines as well as primary cells was monitored by fluorescence microscopy. To determine the appropriate peptide-plasmid charge ratios for efficient cell transfection, electromobility shift assays were carried out. Finally, flow cytometric and fluorescence microscopic studies of gene expression highlighted two novel hCT-derived peptides as highly effective in the delivery of noncovalently complexed plasmid DNA. Thus, the absence of cytotoxicity paired with highly efficient cell internalisation and transfection rates, in primary cells as well, make both peptides powerful candidates as drug delivery vectors, especially for plasmid DNA, for both in vivo and ex vivo therapeutic applications.     

Silicon Substitution for Aluminum in Calcium Silicate Hydrates

²⁷Al MAS and multiquantum (MQ) MASNMR (magic-angle spinning nuclear magnetic resonance) spectroscopy were used to study the substitution of silicon by aluminum in calcium silicate hydrates (C-S-H), which are the main component of hydrated portland cement. Synthetic C-S-H samples were prepared, and their chemical stability was studied. Two-dimensional 3Q-MASNMR spectra revealed the chemical shift and quadrupolar parameters (delta_iso, nu_Q) that labeled aluminum sites in the C-S-H. Tetrahedral aluminum was observed in the bridging and nonbridging sites of the silicate chains.     

Relationship between structure and rheological,mechanical and thermal properties of polylactide/Cloisite 30B nanocomposites

Melt‐state and solid state mechanical properties and thermal stability of polylactide layered silicate nanocomposites elaborated by melt intercalation were studied as a function of clay content. Wide angle X‐ray scattering results, transmission electron microscopy observations, and rheological measurements indicated that the clay was finely distributed in the polylactide matrix. Contrary to nonlinear mechanical properties, thermal and linear mechanical properties were shown to increase with increasing clay fraction. The nanoindentation measurements confirm the significant increase of linear mechanical properties previously observed by tensile tests. The good correlation of linear mechanical properties at the macrometric and nanometric scales is explained by the high dispersion degree of the nanofiller in the biodegradable polymer matrix. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Calcium carbonate and ammonium polyphosphate flame retardant additives formulated to protect ethylene vinyl acetate copolymer against fire: Hydrated or carbonated calcium?

In this study, the effect of the chemical nature of different calcium (Ca)-based minerals as flame retardant additives in combination with ammonium polyphosphate (APP), in 1:1 proportions, on the flame retardancy behavior and performance of ethylene vinyl acetate copolymer was discussed. Combining APP with partly and completely hydrated calcium oxide led to superior flame-retardant function detected in mass loss calorimeter measurements with respect to the corresponding system containing carbonated calcium. This privileged character was attributed to the higher reactivity of hydrated Ca-based fillers toward APP in comparison with Ca carbonate, which induced the formation of an intumescent residue. The difference between reactivity potential of hydrated and dry Ca was demonstrated by the newly formed thermally stable species, and further evidenced by thermogravimetric analysis performed on APP/fillers blends. Moreover, the presence of more crystalline domains in the Ca/phosphorus-based compounds was evidenced by XRD analysis of the mass loss calorimeter test residues. The results of this work highlight the role of blend additive systems on the performance of flame retardancy of polymer materials.     

Development of Covalent Chitosan-Polyethylenimine Derivatives as Gene Delivery Vehicle: Synthesis,Characterization, and Evaluation

There is an increasing interest in cationic polymers as important constituents of non-viral gene delivery vectors. In the present study, we developed a versatile synthetic route for the production of covalent polymeric conjugates consisting of water-soluble depolymerized chitosan (dCS; M_W 6–9 kDa) and low molecular weight polyethylenimine (PEI; 2.5 kDa linear, 1.8 kDa branched). dCS-PEI derivatives were evaluated based on their physicochemical properties, including purity, covalent bonding, solubility in aqueous media, ability for DNA condensation, and colloidal stability of the resulting polyplexes. They were complexed with non-integrating DNA vectors coding for reporter genes by simple admixing and assessed in vitro using liver-derived HuH-7 cells for their transfection efficiency and cytotoxicity. Using a rational screening cascade, a lead compound was selected (dCS-Suc-LPEI-14) displaying the best balance of biocompatibility, cytotoxicity, and transfection efficiency. Scale-up and in vivo evaluation in wild-type mice allowed for a direct comparison with a commercially available non-viral delivery vector (in vivo-jetPEI). Hepatic expression of the reporter gene luciferase resulted in liver-specific bioluminescence, upon intrabiliary infusion of the chitosan-based polyplexes, which exceeded the signal of the in vivo jetPEI reference formulation by a factor of 10. We conclude that the novel chitosan-derivative dCS-Suc-LPEI-14 shows promise and potential as an efficient polymeric conjugate for non-viral in vivo gene therapy.     

Stable dye-sensitized solar cells based on organic chromophores and ionic liquid electrolyte

A series of polyene-diphenylaniline based organic dyes (coded as D5, D7, D9 and D11) have been reported for the application in ionic liquid electrolyte based dye-sensitized solar cells. The effects of substitution of organic dyes on the photovoltaic performance have been investigated, which show addition of methoxy groups on the triphenylamine donor group increases short-circuit current, open-circuit voltage and photovoltaic performance. A power conversion efficiency of 6.5% under AM 1.5 sunlight at 100 mW/cm² has been obtained with D11 dye in combination with a binary ionic liquid electrolyte, which when subjected to accelerated testing under one sun light soaking at 60 °C, the efficiency remained 90% of initial efficiency.