Copper complexes of new benzodioxotetraaza macrocycles with potential applications in nuclear medicine

Two novel benzodioxotetraaza macrocycles [2,9-dioxo-1,4,7,10-tetraazabicyclo[10.4.0]1,11-hexadeca-1(11),13,15-triene (H(2)L1) and 2,10-dioxo-1,4,8,11-tetraazabicyclo[11.4.0]1,12-heptadeca-1(12),14,16-triene (H(2)L2)] were synthesized by a [1 + 1] crablike cyclization. The protonation constants of both ligands were determined by H-1 NMR titration and by potentiometry at 25.0 degrees C in 0.10 M ionic strength in KNO3. The latter method was also used to ascertain the stability constants of their copper(II) complexes. These studies showed that the CuL1 complex has a much lower thermodynamic stability than the CuL2, and the H(2)L2 displays an excellent affinity for copper(II), due to the good fit of copper(II) into its cavity. The copper complexes of the novel ligands were characterized by electronic spectroscopy in solution and by crystal X-ray diffraction. These studies indicated that the copper center in the CuL1 complex adopts a square-pyramidal geometry with the four nitrogen atoms of the macrocycle forming the equatorial plane and a water molecule at axial position, and the copper in the CuL2 complex is square-planar. Several labeling conditions were tested, and only H(2)L2 could be labeled with Cu-67 efficiently (> 98%) in mild conditions (39 degrees C, 15 min) to provide a slightly hydrophilic radioligand (log D = -0.19 +/- 0.03 at pH 7.4). The in vitro stability was studied in the presence of different buffers or with an excess of diethylenetriamine-pentaethanoic acid. Very high stability was shown under these conditions for over 5 days. The incubation of the radiocopper complex in human serum showed 6% protein binding.

Supramolecular hydrogen-bond structures and magnetic interactions in basal-apical, dinuclear, azide-bridged copper(II) complexes

The synthesis, characterisation, X-ray single crystal structures and magnetic properties of three new basal-apical mu(2)-1,1-azide-bridged complexes [(CuLN3)-N-1](2) (1), [(CuLN3)-N-2](2) (2) and [(CuLN3)-N-3](2) (3) with very similar tridentate Schiff-base blocking ligands {HL1 = N-[2-(ethylamino) ethyl] salicylaldimine; HL2 = 7-(ethylamino)-4-methyl-5-azahept-3-en-2-one; HL3 = 7-amino-4-methyl-5-azaoct-3-en-2-one} have been reported [complex 1: monoclinic, P2(1)/c, a = 8.390(2), b = 7.512(2), c = 19.822(6) Angstrom, beta = 91.45(5)degrees; complex 2: monoclinic, P2(1)/c, a = 8.070(9), b = 9.787(12), c = 15.743(17) A, beta = 98.467(10)degrees; complex 3: monoclinic, P2(1)/n, a = 5.884(7), b = 16.147(18), c = 11.901(12) Angstrom, beta = 90.050(10)degrees]. The structures consist of neutral dinuclear entities resulting from the pairing of two mononuclear units through end-on azide bridges connecting an equatorial position of one copper centre to an axial position of the other, The copper ions adopt a (4+1) square-based geometry in all the complexes. In complex 2, there is no inter-dimer hydrogen-bonding. However, complexes 1 and 3 form two different supramolecular structures in which the dinuclear entities are linked by H-bonds giving one-dimensional systems. Variable temperature (300-2 K) magnetic-susceptibility measurements and magnetisation measurements at 2 K reveal that all three complexes have antiferromagnetic coupling. Magneto-structural correlations have been made taking into consideration both the azido bridging ligands and the existence of intermolecular hydrogen bonds. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Rice seed quality development and temperature during late development and maturation

The potential longevity of japonica rice (Oryza sativa L. subsp. japonica) seed is particularly sensitive to high temperature – and thus climate change – during development and maturation. Cultivar Taipei 309 was grown at 28/208C (12 h/12 h) and then from 19 DAA (days after 50% anthesis), when seeds were just over half filled, at 28/208C, 30/228C, 32/248C or 34/268C (12 h/12 h). Whereas ability to germinate ex planta had been achieved in almost all seeds by 24 DAA, only half the population were desiccation tolerant. Desiccation tolerance continued to increase over the subsequent 28 d, similarly at all four temperatures. Subsequent longevity, assessed by p50 (period in days to reduce viability to 50% in hermetic storage at 408C with c. 15% moisture content), increased progressively at 28/208C until 38 DAA, and remained constant until the final harvest (52 DAA). The three warmer temperature regimes provided similar longevity to 28/208C at any one harvest, except at 38 DAA where the warmest (34/268C) was poorer. That temperature regime also provided greater seed-to-seed variability within each survival curve. The results confirm that appreciable improvement in seed quality occurs during seed development and also subsequent maturation in japonica rice, but that increase in temperature from 28/208C to 34/268C during late seed filling onwards has comparatively little effect thereon. Comparison with previous investigations suggests that seed quality development may be less sensitive to high temperatures during late development and maturation than during the early seed development that precedes it.

Carbamazepine trifluoroacetic acid solvate

Carbamazepine forms a 1:1 solvate with trifluoroacetic acid (systematic name: 5H-dibenzo[b,f] azepine-5-carboxamide trifluoroacetic acid solvate), C(15)H(12)N(2)O center dot C(2)HF(3)O(2). The compound crystallizes with one molecule of carbamazepine and one of trifluoroacetic acid in the asymmetric unit to form an R(2)(2)(8) motif. The solvent molecule is disordered over two sites, with site-occupancy factors 0.53 (1) and 0.47 (1).

Configurational preferences of two 1,2-diamine adducts of bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)

The preparation, the IR and ligand field spectra and the structures of the mixed-ligand addition compounds [(N,N-dimethyl-1,2-diaminoethane)bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)], [Co(thtf)2me2en], and [(N,N,N′,N′-tetramethyl-1,2-diaminoethane)bis(1-(2-thienyl)-4,4,4-trifluoro-1,3-butanedionato)cobalt(II)], [Co(thtf)2me4en], are reported. The structures were determined by single crystal X-ray diffraction analysis (monoclinic, space group P21/c, Z=4 with a=10.708(6), b=19.531(6), c=13.352(6) Å, β=111.64(10)°, R1=0.0642 and wR2=0.1719 for [Co(thtf)2(me2en)] and a=12.033(6), b=15.565(6), c=15.339(6) Å, β=92.57(6)°, R1=0.0612 and wR2=0.1504 for [Co(thtf)2me4en]). The structures are distorted octahedral and the shortest cobalt–cobalt separation distances are 5.388(2) Å in [Co(thtf)2me2en] and 8.675(3) Å in [Co(thtf)2me4en]. In both compounds the diamine molecules attain the gauche conformation. The U(Z,Z) conformation of the β-dione leads to a semi-chair conformation of the β-dionato chelate rings. The relative orientation of the groups attached to the β-dionato moiety depends on the extent of stereoelectronic effects the N-substitution of the diamine entails. In [Co(thtf)2me2en] the intraligand distance separating the trifluoromethyl carbon atoms is 5.281(18) Å while in [Co(thtf)2me2en] it increases to 8.338(9) Å. The cobalt–cobalt separation distance, the orientation of the chelate rings and the extent of N-substitution seem to affect hydrogen bonding. While in [Co(thtf)2me2en] inter- and intraligand hydrogen bonding is implicated, it is totally absent in [Co(thtf)2me4en].

Is there sufficient 'sink' in current bioaccessibility determinations of organic pollutants in soils?

Bioaccessibility tests can be used to improve contaminated land risk assessments. For organic pollutants a ‘sink’ is required within these tests to better mimic their desorption under the physiological conditions prevailing in the intestinal tract, where a steep diffusion gradient for the removal of organic pollutants from the soil matrix would exist. This is currently ignored in most PBET systems. By combining the CEPBET bioaccessibility test with an infinite sink, the removal of PAH from spiked solutions was monitored. Less than 10% of spiked PAH remained in the stomach media after 1 h, 10% by 4 h in the small intestine compartment and c.15% after 16 h in the colon. The addition of the infinite sink increased bioaccessibility estimates for field soils by a factor of 1.2–2.8, confirming its importance for robust PBET tests. TOC or BC were not the only factors controlling desorption of the PAH from the soils.

Oppida, agglomerations and suburbia: the bibracte environs and new perspectives on late Iron Age urbanism in central-eastern France

This paper explores the nature and chronology of La Tène and early Roman unenclosed agglomerations in central-eastern France. It has been prompted by the discovery of a c. 115 ha La Tène D2b/Augustan (c. 50 bc to ad 15) site close to Bibracte in the Morvan, located around the source of the River Yonne. This complex provides a new perspective on the chronology and role of Late La Tène and early Roman unenclosed settlements, adding further complexity to the story of the development of Late La Tène oppida. It indicates that these ‘agglomerations’ followed remarkably varied chronological trajectories, raising important issues concerning the nature of landscape and social change at the end of the Iron Age. Dieser Aufsatz untersucht den Charakter und die Datierung von latènezeitlichen und frührömischen offenen Siedlungen im östlichen Zentralfrankreich. Die Anregung dazu erfolgte durch die Entdeckung einer Latène D2b-zeitlichen bis augusteischen (ca. 50 v. Chr. – 15 n. Chr.) Anlage im Morvan bei Bibracte, die ca. 115 ha Fläche bedeckt und sich um die Quellen des Flusses Yonne erstreckt. Es wird vorgeschlagen, dass dieser Siedlungskomplex eine Ergänzung, aber auch einen Kontrast zu den üblichen Interpretationsmodellen von spätlatènezeitlichen und frührömischen, offenen Großsiedlungen und ihrer zeitlichen Entwicklung darstellt, und weiter zur Komplexität der Entwicklung spätlatènezeitlicher Oppida beiträgt. Es deutet sich an, dass einige der ‘Agglomerationen’ anderen Entwicklungslinien folgen, die wichtige Fragen zur Landschaftsgenese und zum sozialen Wandel am Ende der Eisenzeit aufwerfen. Cet article a pour but d'explorer la nature ainsi que la chronologie des agglomérations ouvertes apparaissant à La Tène Final et au début de la période gallo-romaine du Centre-Est de la France. Il fut inspiré et écrit suite à la découverte dans le Morvan d'un site de 115 ha datant de La Tène D2b et de la période Augustéenne (50 av. J.C. à 15 ap. J.C.) s'étirant autour des Sources de l'Yonne. Cette agglomération apporte de nouvelles perspectives sur la chronologie et sur le rôle des habitats ouverts à la fin de l'Âge du Fer ainsi qu'au début de l'époque gallo-romaine apportant des éléments amenés à renforcer le caractère complexe de l'histoire du développement des oppida à La Tène Final. Cette synthèse tend à démontrer que ces agglomérations suivaient des trajectoires chronologiques variées, élevant un certain nombre de questions, et donc des nouvelles problématiques, concernant la nature du paysage et du changement social à la fin de l'Âge du Fer.

Polymorphism and optical properties in [NH4][InSe2]

The solvothermal synthesis and characterization of two indium selenides with stoichiometry [NH4][InSe2] is described. Yellow [NH4][InSe2] (1), which exhibits a layered structure, was initially prepared in an aqueous solution of trans-1,4-diaminocyclohexane, and subsequently using a concentrated ammonia solution. A red polymorph of one-dimensional character, [NH4][InSe2] (2), was obtained using 3,5-dimethylpyridine as solvent. [NH4][InSe2] (1) crystallizes in the non-centrosymmetric space group Cc (a=11.5147(6), b=11.3242(6), c=15.9969(9) Å and β=100.354(3)°). The structural motif of the layers is the In4Se10 adamantane unit, composed of four corner-linked InSe4 tetrahedra. These units are linked by their corners, forming [InSe2]− layers which are stacked back to back along the c-direction, and interspaced by [NH4]+cations. The one-dimensional polymorph, (2), crystallizes in the tetragonal space group, I4/mcm (a=8.2519(16), c=6.9059 (14) Å). This structure contains infinite chains of edge-sharing InSe4 tetrahedra separated by [NH4]+ cations.

Effect of high pressure homogenisation and heat treatment on physical properties and stability of almond and hazelnut milks

The effect of high pressure homogenisation (HPH) and heat treatments on physicochemical properties and physical stability of almond and hazelnut milks was studied. Vegetable milks were obtained and homogenised by applying 62, 103 and 172 MPa (MF1, MF2 and MF3, respectively). Untreated and MF3 samples were also submitted to two different heat treatments (85 °C/30 min (LH) or 121 °C/15 min (HH)). Physical and structural properties of the products were greatly affected by heat treatments and HPH. In almond milk, homogenised samples showed a significant reduction in particle size, which turned from bimodal and polydisperse to monodisperse distributions. Particle surface charge, clarity and Whiteness Index were increased and physical stability of samples was improved, without affecting either viscosity or protein stability. Hazelnut beverages showed similar trends, but HPH notably increased their viscosity while change their rheological behaviour, which suggested changes in protein conformation. HH treatments caused an increment of particle size due to the formation oil droplet-protein body clusters, associated with protein denaturation. Samples submitted to the combined treatment MF3 and LH showed the greatest stability.

Effect of simulated rainfall during wheat seed development and maturation on subsequent seed longevity is reversible

Poor wheat seed quality in temperate regions is often ascribed to wet production environments. We investigated the possible effect of simulated rain during seed development and maturation on seed longevity in wheat (Triticum aestivum L.) cv. Tybalt grown in the field (2008, 2009) or a polythene tunnel house (2010). To mimic rain, the seed crops were wetted from above with the equivalent of 30mm (2008, 2009) or 25mm rainfall (2010) at different stages of seed development and maturation (17 to 58 DAA, days after 50% anthesis), samples harvested serially, and subsequent air-dry seed longevity estimated. No pre-harvest sprouting occurred. Seed longevity (p50, 50% survival period in experimental hermetic storage at 40°C with c. 15% moisture content) in field-grown controls increased during seed development and maturation attaining maxima at 37 (2008) or 44 DAA (2009); it declined thereafter. Immediate effects of simulated rain at 17-58 DAA in field studies (2008, 2009) on subsequent seed longevity were negative but small, e.g. a 1-4 d delay in seed quality improvement for treatments early in development but with no damage detected at final harvests. In rainfall-protected conditions (2010), simulated rain close to harvest maturity (55-56 DAA) reduced longevity immediately and substantially, with greater damage from two sequential days of wetting than one; again, later harvests provided evidence of recovery in subsequent longevity. In the absence of pre-harvest sprouting, the potentially deleterious effects of rainfall to wheat seed crops on subsequent seed longevity may be reversible in full or in part.

Carbon (C-13) and nitrogen (N-15) translocation in a maize-Striga hermonthica association

The translocation of C and N in a maize-Striga hermonthica association was investigated at three rates of nitrogen application in a glasshouse experiment. The objectives were to measure the transfer of C and N from maize to S. hermonthica and to determine whether the amount of N in the growing medium affected the proportions of C and N transferred. Young plants of maize were labelled in a (CO2)-C-13 atmosphere and leaf tips were immersed in ((NH4)-N-15)(2)SO4 Solution. The Striga x N interaction was not significant for any of the responses measured. Total dry matter for infected maize was significantly smaller than for uninfected maize from 43 to 99 days after planting, but N application increased total dry matter at all sampling times. Infected maize plants partitioned 39-45 % of their total dry matter to the roots compared with 28-31 % for Uninfected maize. Dry matter of S. hermonthica was not affected by the rate of N applied. S. hermonthica derived 100 % of its carbon from maize before emergence, decreasing to 22-59 % thereafter; the corresponding values for nitrogen were up to 59 % pre-emergence and Lip to 100 % after emergence. The relative proportions of nitrogen depleted from the host (up to 10 %) were greater than those of carbon (maximum 1.2 %) at all times of sampling after emergence of the parasite. The results show that the parasite was more dependent on the host for nitrogen than for carbon.

Carbon (C-13) and nitrogen (N-15) translocation in a maize-Striga hermonthica association

The translocation of C and N in a maize-Striga hermonthica association was investigated at three rates of nitrogen application in a glasshouse experiment. The objectives were to measure the transfer of C and N from maize to S. hermonthica and to determine whether the amount of N in the growing medium affected the proportions of C and N transferred. Young plants of maize were labelled in a (CO2)-C-13 atmosphere and leaf tips were immersed in ((NH4)-N-15)(2)SO4 Solution. The Striga x N interaction was not significant for any of the responses measured. Total dry matter for infected maize was significantly smaller than for uninfected maize from 43 to 99 days after planting, but N application increased total dry matter at all sampling times. Infected maize plants partitioned 39-45 % of their total dry matter to the roots compared with 28-31 % for Uninfected maize. Dry matter of S. hermonthica was not affected by the rate of N applied. S. hermonthica derived 100 % of its carbon from maize before emergence, decreasing to 22-59 % thereafter; the corresponding values for nitrogen were up to 59 % pre-emergence and Lip to 100 % after emergence. The relative proportions of nitrogen depleted from the host (up to 10 %) were greater than those of carbon (maximum 1.2 %) at all times of sampling after emergence of the parasite. The results show that the parasite was more dependent on the host for nitrogen than for carbon.

Evaluating the century C model using long-term fertilizer trials in the Indo-Gangetic Plains, India

The GEFSOC Project developed a system for estimating soil carbon (C) stocks and changes at the national and sub-national scale. As part of the development of the system, the Century ecosystem model was evaluated for its ability to simulate soil organic C (SOC) changes in environmental conditions in the Indo-Gangetic Plains, India (IGP). Two long-term fertilizer trials (LTFT), with all necessary parameters needed to run Century, were used for this purpose: a jute (Corchorus capsularis L.), rice (Oryza sativa L.) and wheat (Triticum aestivum L.) trial at Barrackpore, West Bengal, and a rice-wheat trial at Ludhiana, Punjab. The trials represent two contrasting climates of the IGP, viz. semi-arid, dry with mean annual rainfall (MAR) of < 800 mm and humid with > 1600 turn. Both trials involved several different treatments with different organic and inorganic fertilizer inputs. In general, the model tended to overestimate treatment effects by approximately 15%. At the semi-arid site, modelled data simulated actual data reasonably well for all treatments, with the control and chemical N + farm yard manure showing the best agreement (RMSE = 7). At the humid site, Century performed less well. This could have been due to a range of factors including site history. During the study, Century was calibrated to simulate crop yields for the two sites considered using data from across the Indian IGP. However, further adjustments may improve model performance at these sites and others in the IGP. The availability of more longterm experimental data sets (especially those involving flooded lowland rice and triple cropping systems from the IGP) for testing and validation is critical to the application of the model's predictive capabilities for this area of the Indian sub-continent. (C) 2007 Elsevier B.V. All rights reserved.

Is 15 per cent very common? Informing people about the risks of medication side effects

Objectives - To assess the general public's interpretation of the verbal descriptors for side effect frequency recommended for use in medicine information leaflets by a European Union (EU) guideline, and to examine the extent to which differences in interpretation affect people's perception of risk and their judgments of intention to comply with the prescribed treatment. Method - Two studies used a controlled empirical methodology in which people were presented with a hypothetical, but realistic, scenario about visiting their general practitioner and being prescribed medication. They were given an explanation that focused on the side effects of the medicine, together with information about the probability of occurrence using either numerical percentages or the corresponding EU verbal descriptors. Interpretation of the descriptors was assessed. In study 2, participants were also required to make various judgments, including risk to health and intention to comply. Key findings - In both studies, use of the EU recommended descriptors led to significant overestimations of the likelihood of particular side effects occurring. Study 2 further showed that the "overestimation" resulted in significantly increased ratings of perceived severity of side effects and risk to health, as well as significantly reduced ratings of intention to comply, compared with those for people who received the probability information in numerical form. Conclusion - While it is recognised that the current findings require replication in a clinical setting, the European and national authorities should suspend the use of the EU recommended terms until further research is available to allow the use of an evidence-based approach.