Synthesis of alpha-amino acid derived (1,2,3-triazol-4-yl)-picolinamide (tzpa) ligands and their corresponding luminescent Tb(iii) complexes

The synthesis of chiral a-amino acid derived (1,2,3-triazol-4-yl)-picolinamide (tzpa) ligands 4-6 designed by combining the coordination properties of two well-known ligand structures within a single unit is described. The self-assembly formation between these ligands and the lanthanide ion Tb(iii) was investigated in solution by probing the ground and the singlet excited state properties of the ligands as well as monitoring the evolution of the Tb(iii) emission at long wavelengths. The spectroscopic results showed that while under thermodynamic control the 1 : 3 (Tb : L) is produced, then analysis of the titration data using non-liner regression analysis demonstrated that the main species in solution is the 1 : 2 (Tb : L) after the addition of 0.5 equivalents of Tb(iii)

Norbornene chaotropic salts as low molecular mass ionic organogelators (LMIOGs)

Phenylalanine functionalised norbornene (9:Na) functions as a potent, low molecular-mass (MW = 333 Da) ionic organogelator with a minimum gelating concentration of 0.5 wt% in THF, i-PrOH, 1,4-dioxane and n-BuOH. Fibrous crystals form in the gel and X-ray crystallography identified a cation mediated helical assembly process controlled by the chirality of the phenylalanine. In additon to excellent gelating properties 9:Na readily forms aqueous biphasic and triphasic systems

Distribution and abundance of long-finned pilot whales in the North Atlantic, estimated from NASS-87 and NASS-89 data

During the summers of 1987 and 1989, large scale transect surveys were conducted throughout the North Atlantic by several national agencies in Denmark (off Greenland), Faroe Islands, Iceland, Norway and Spain (North Atlantic Sightings Surveys, NASS-87 and NASS-89). This paper analyses the pilot whale (Globicephala melas) survey data collected by three Icelandic and one Faroese survey vessel in 1987, and four Icelandic, one Faroese and one Spanish vessel in 1989. Norwegian survey vessels operated north and east of this area in both years, but only five groups (three primary sightings) were observed in 1989 and none in 1987. Furthermore, no sightings were made in the area north and northeast of Iceland, thus indicating that the joint surveys covered the northernmost areas of pilot whale distribution east of 42°W. The area further to the west was not covered in either survey. The coastal European waters between 42-52°N were covered by the Spanish vessel in 1989. Sightings made in 1989 by the Icelandic vessels tended to be at the southernmost boundaries of the survey area. The present data were examined with respect to several potential stratification factors, namely geographic block, Beaufort (i.e. wind speed), vessel and school size, but sample size precluded stratification by all these factors simultaneously. The encounter rate was generally lower in the 1987 survey than in 1989, but the difference was not statistically significant. The total estimate for the 1989 survey, covering a wider area and further to the south than in 1987, was 778,000 (CV=0.295). This is regarded as the best available estimate of the total stock of long-finned pilot whales in the northeastern North Atlantic Ocean, although small numbers occur outside the NASS survey areas. The paper discusses potential biases in the abundance estimates, and the problems of estimating pilot whale abundance from sightings data

Tripodal 1,3,5-benzenetricarboxamide ligand with dipicolinic acid units and its binding with Eu(III) ions

The synthesis and characterisation of tripodal ligand 1 containing 1,3,5-benzenetricarboxamide core and diethyl 4-(phenylethynyl)pyridine-2,6-dicarboxylate is described. The crystal structure of the intermediate tripodal molecule 7 exhibits an unusual staggered hydrogen-bonded chain motif instead of the anticipated helical assembly. We studied the basic photophysical properties of 1 in solvents of various polarity including CH3OH, CH3CN, DMSO, and CHCl3. The self-assembly experiments between 1 and Eu(CF3SO3)3⋅6H2O confirmed the formation of metal-ligand self-assembly species in the solution of CH3CN. It was also shown that the excitation of the Eu(III)-centred emission in such species occurred through the energy transfer from the ligand acting as an antenna to the metal centre. The binding constant values were evaluated using the nonlinear regression analysis software SPECFIT®, and their values correspond to those previously observed for the assemblies between 2,6-dipicolinic acid derivatives and lanthanide ions. This work describes the synthesis of tripodal 1,3,5-benzenetricarboxamide ligand with dipicolinic acid units and its binding with Eu(III) ions in solution. The photophysical properties of the target tripodal ligand were studied in solvents of various polarity. The self-assembly experiments between the ligand and Eu(III) ions in solution confirmed the formation of luminescent metal-ligand self-assembly species.</p

Fluorescent chemosensors: The past, present and future

Fluorescent chemosensors for ions and neutral analytes have been widely applied in many diverse fields such as biology, physiology, pharmacology, and environmental sciences. The field of fluorescent chemosensors has been in existence for about 150 years. In this time, a large range of fluorescent chemosensors have been established for the detection of biologically and/or environmentally important species. Despite the progress made in this field, several problems and challenges still exist. This tutorial review introduces the history and provides a general overview of the development in the research of fluorescent sensors, often referred to as chemosensors. This will be achieved by highlighting some pioneering and representative works from about 40 groups in the world that have made substantial contributions to this field. The basic principles involved in the design of chemosensors for specific analytes, problems and challenges in the field as well as possible future research directions are covered. The application of chemosensors in various established and emerging biotechnologies, is very bright. © 2017 The Royal Society of Chemistry

The effect on the small bowel of 5-FU and oxaliplatin in combination with radiation using a microcolony survival assay

<p>Abstract</p> <p>Background</p> <p>In locally advanced rectal cancer, 5-Fluorouracil (5-FU)-based chemoradiation is the standard treatment. The main acute toxicity of this treatment is enteritis. Due to its potential radiosensitizing properties, oxaliplatin has recently been incorporated in many clinical chemoradiation protocols. The aim of this study was to investigate to what extent 5-FU and oxaliplatin influence the radiation (RT) induced small bowel mucosal damage when given in conjunction with single or split dose RT.</p> <p>Methods</p> <p>Immune competent balb-c mice were treated with varying doses of 5-FU, oxaliplatin (given intraperitoneally) and total body RT, alone or in different combinations in a series of experiments. The small bowel damage was studied by a microcolony survival assay. The treatment effect was evaluated using the inverse of the slope (D₀) of the exponential part of the dose-response curve.</p> <p>Results</p> <p>In two separate experiments the dose-response relations were determined for single doses of RT alone, yielding D₀values of 2.79 Gy (95% CI: 2.65 - 2.95) and 2.98 Gy (2.66 - 3.39), for doses in the intervals of 5-17 Gy and 5-10 Gy, respectively. Equitoxic low doses (IC5) of the two drugs in combination with RT caused a decrease in jejunal crypt count with significantly lower D₀: 2.30 Gy (2.10 - 2.56) for RT+5-FU and 2.27 Gy (2.08 - 2.49) for RT+oxaliplatin. Adding both drugs to RT did not further decrease D₀: 2.28 Gy (1.97 - 2.71) for RT+5-FU+oxaliplatin. A clearly higher crypt survival was noted for split course radiation (3 × 2.5 Gy) compared to a single fraction of 7.5 Gy. The same difference was seen when 5-FU and/or oxaliplatin were added.</p> <p>Conclusion</p> <p>Combining 5-FU or oxaliplatin with RT lead to an increase in mucosal damage as compared to RT alone in our experimental setting. No additional reduction of jejunal crypt counts was noted when both drugs were combined with single dose RT. The higher crypt survival with split dose radiation indicates a substantial recovery between radiation fractions. This mucosal-sparing effect achieved by fractionation was maintained also when chemotherapy was added.</p