Complexes of lanthanide perchlorates with two new " O,N,O " ligands derived from antipyraldehyde and acetic and benzoic acid hydrazides

Antipyrlne is a well known llgand for lanthanldes (i). A forage through the organic literature of pyrazolones reveals that the 4-position of antipyrlne is amenable to a wide variety of organic reactions. It should thus be possible to introduce suitable functional groups at this position and design new multidentate ligands for metal ions. It is also found that the coordination chemistry of lanthanides is much less well developed and far fewer ligands have been used for complexation with lanthanide ions compared to that of the d-transition metal ions.

Harvest strategy evaluations and co-management for the Moreton Bay Trawl Fishery

Non-Technical Summary Seafood CRC Project 2009/774. Harvest strategy evaluations and co-management for the Moreton Bay Trawl Fishery Principal Investigator: Dr Tony Courtney, Principal Fisheries Biologist Fisheries and Aquaculture, Agri-Science Queensland Department of Agriculture, Fisheries and Forestry Level B1, Ecosciences Precinct, Joe Baker St, Dutton Park, Queensland 4102 Email: tony.courtney@daff.qld.gov.au Project objectives: 1. Review the literature and data (i.e., economic, biological and logbook) relevant to the Moreton Bay trawl fishery. 2. Identify and prioritise management objectives for the Moreton Bay trawl fishery, as identified by the trawl fishers. 3. Undertake an economic analysis of Moreton Bay trawl fishery. 4. Quantify long-term changes to fishing power for the Moreton Bay trawl fishery. 5. Assess priority harvest strategies identified in 2 (above). Present results to, and discuss results with, Moreton Bay Seafood Industry Association (MBSIA), fishers and Fisheries Queensland. Note: Additional, specific objectives for 2 (above) were developed by fishers and the MBSIA after commencement of the project. These are presented in detail in section 5 (below). The project was an initiative of the MBSIA, primarily in response to falling profitability in the Moreton Bay prawn trawl fishery. The analyses were undertaken by a consortium of DAFF, CSIRO and University of Queensland researchers. This report adopted the Australian Standard Fish Names (http://www.fishnames.com.au/). Trends in catch and effort The Moreton Bay otter trawl fishery is a multispecies fishery, with the majority of the catch composed of Greasyback Prawns (Metapenaeus bennettae), Brown Tiger Prawns (Penaeus esculentus), Eastern King Prawns (Melicertus plebejus), squid (Uroteuthis spp., Sepioteuthis spp.), Banana Prawns (Fenneropenaeus merguiensis), Endeavour Prawns (Metapenaeus ensis, Metapenaeus endeavouri) and Moreton Bay bugs (Thenus parindicus). Other commercially important byproduct includes blue swimmer crabs (Portunus armatus), three-spot crabs (Portunus sanguinolentus), cuttlefish (Sepia spp.) and mantis shrimp (Oratosquilla spp.). Logbook catch and effort data show that total annual reported catch of prawns from the Moreton Bay otter trawl fishery has declined to 315 t in 2008 from a maximum of 901 t in 1990. The number of active licensed vessels participating in the fishery has also declined from 207 in 1991 to 57 in 2010. Similarly, fishing effort has fallen from a peak of 13,312 boat-days in 1999 to 3817 boat-days in 2008 – a 71% reduction. The declines in catch and effort are largely attributed to reduced profitability in the fishery due to increased operational costs and depressed prawn prices. The low prawn prices appear to be attributed to Australian aquacultured prawns and imported aquacultured vannamei prawns, displacing the markets for trawl-caught prawns, especially small species such as Greasyback Prawns which traditionally dominated landings in Moreton Bay. In recent years, the relatively high Australian dollar has resulted in reduced exports of Australian wild-caught prawns. This has increased supply on the domestic market which has also suppressed price increases. Since 2002, Brown Tiger Prawns have dominated annual reported landings in the Moreton Bay fishery. While total catch and effort in the bay have declined to historically low levels, the annual catch and catch rates of Brown Tiger Prawns have been at record highs in recent years. This appears to be at least partially attributed to the tiger prawn stock having recovered from excessive effort in previous decades. The total annual value of the Moreton Bay trawl fishery catch, including byproduct, is about $5 million, of which Brown Tiger Prawns account for about $2 million. Eastern King Prawns make up about 10% of the catch and are mainly caught in the bay from October to December as they migrate to offshore waters outside the bay where they contribute to a large mono-specific trawl fishery. Some of the Eastern King Prawns harvested in Moreton Bay may be growth overfished (i.e., caught below the size required to maximise yield or value), although the optimum size-at-capture was not determined in this study. Banana Prawns typically make up about 5% of the catch, but can exceed 20%, particularly following heavy rainfall. Economic analysis of the fishery From the economic survey, cash profits were, on average, positive for both fleet segments in both years of the survey. However, after the opportunity cost of capital and depreciation were taken into account, the residual owner-operator income was relatively low, and substantially lower than the average share of revenue paid to employed skippers. Consequently, owner-operators were earning less than their opportunity cost of their labour, suggesting that the fleets were economically unviable in the longer term. The M2 licensed fleet were, on average, earning similar boat cash profits as the T1/M1 fleet, although after the higher capital costs were accounted for the T1/M1 boats were earning substantially lower returns to owner-operator labour. The mean technical efficiency for the fleet as a whole was estimated to be 0.67. That is, on average, the boats were only catching 67 per cent of what was possible given their level of inputs (hours fished and hull units). Almost one-quarter of observations had efficiency scores above 0.8, suggesting a substantial proportion of the fleet are relatively efficient, but some are also relatively inefficient. Both fleets had similar efficiency distributions, with median technical efficiency score of 0.71 and 0.67 for the M2 and T1/M1 boats respectively. These scores are reasonably consistent with other studies of prawn trawl fleets in Australia, although higher average efficiency scores were found in the NSW prawn trawl fleet. From the inefficiency model, several factors were found to significantly influence vessel efficiency. These included the number of years of experience as skipper, the number of generations that the skipper’s family had been fishing and the number of years schooling. Skippers with more schooling were significantly more efficient than skippers with lower levels of schooling, consistent with other studies. Skippers who had been fishing longer were, in fact, less efficient than newer skippers. However, this was mitigated in the case of skippers whose family had been involved in fishing for several generations, consistent with other studies and suggesting that skill was passed through by families over successive generations. Both the linear and log-linear regression models of total fishing effort against the marginal profit per hour performed reasonably well, explaining between 70 and 84 per cent of the variation in fishing effort. As the models had different dependent variables (one logged and the other not logged) this is not a good basis for model choice. A better comparator is the square root of the mean square error (SMSE) expressed as a percentage of the mean total effort. On this criterion, both models performed very similarly. The linear model suggests that each additional dollar of average profits per hour in the fishery increases total effort by around 26 hours each month. From the log linear model, each percentage increase in profits per hour increases total fishing effort by 0.13 per cent. Both models indicate that economic performance is a key driver of fishing effort in the fishery. The effect of removing the boat-replacement policy is to increase individual vessel profitability, catch and effort, but the overall increase in catch is less than that removed by the boats that must exit the fishery. That is, the smaller fleet (in terms of boat numbers) is more profitable but the overall catch is not expected to be greater than before. This assumes, however, that active boats are removed, and that these were also taking an average level of catch. If inactive boats are removed, then catch of the remaining group as a whole could increase by between 14 and 17 per cent depending on the degree to which costs are reduced with the new boats. This is still substantially lower than historical levels of catch by the fleet. Fishing power analyses An analysis of logbook data from 1988 to 2010, and survey information on fishing gear, was performed to estimate the long-term variation in the fleet’s ability to catch prawns (known as fishing power) and to derive abundance estimates of the three most commercially important prawn species (i.e., Brown Tiger, Eastern King and Greasyback Prawns). Generalised linear models were used to explain the variation in catch as a function of effort (i.e., hours fished per day), vessel and gear characteristics, onboard technologies, population abundance and environmental factors. This analysis estimated that fishing power associated with Brown Tiger and Eastern King Prawns increased over the past 20 years by 10–30% and declined by approximately 10% for greasybacks. The density of tiger prawns was estimated to have almost tripled from around 0.5 kg per hectare in 1988 to 1.5 kg/ha in 2010. The density of Eastern King Prawns was estimated to have fluctuated between 1 and 2 kg per hectare over this time period, without any noticeable overall trend, while Greasyback Prawn densities were estimated to have fluctuated between 2 and 6 kg per hectare, also without any distinctive trend. A model of tiger prawn catches was developed to evaluate the impact of fishing on prawn survival rates in Moreton Bay. The model was fitted to logbook data using the maximum-likelihood method to provide estimates of the natural mortality rate (0.038 and 0.062 per week) and catchability (which can be defined as the proportion of the fished population that is removed by one unit of effort, in this case, estimated to be 2.5 ± 0.4 E-04 per boat-day). This approach provided a method for industry and scientists to develop together a realistic model of the dynamics of the fishery. Several aspects need to be developed further to make this model acceptable to industry. Firstly, there is considerable evidence to suggest that temperature influences prawn catchability. This ecological effect should be incorporated before developing meaningful harvest strategies. Secondly, total effort has to be allocated between each species. Such allocation of effort could be included in the model by estimating several catchability coefficients. Nevertheless, the work presented in this report is a stepping stone towards estimating essential fishery parameters and developing representative mathematical models required to evaluate harvest strategies. Developing a method that allowed an effective discussion between industry, management and scientists took longer than anticipated. As a result, harvest strategy evaluations were preliminary and only included the most valuable species in the fishery, Brown Tiger Prawns. Additional analyses and data collection, including information on catch composition from field sampling, migration rates and recruitment, would improve the modelling. Harvest strategy evaluations As the harvest strategy evaluations are preliminary, the following results should not be adopted for management purposes until more thorough evaluations are performed. The effects, of closing the fishery for one calendar month, on the annual catch and value of Brown Tiger Prawns were investigated. Each of the 12 months (i.e., January to December) was evaluated. The results were compared against historical records to determine the magnitude of gain or loss associated with the closure. Uncertainty regarding the trawl selectivity was addressed using two selectivity curves, one with a weight at 50% selection (S50%) of 7 g, based on research data, and a second with S50% of 14 g, put forward by industry. In both cases, it was concluded that any monthly closure after February would not be beneficial to the industry. The magnitude of the benefit of closing the fishery in either January or February was sensitive to which mesh selectivity curve that was assumed, with greater benefit achieved when the smaller selectivity curve (i.e., S50% = 7 g) was assumed. Using the smaller selectivity (S50% = 7 g), the expected increase in catch value was 10–20% which equates to $200,000 to $400,000 annually, while the larger selectivity curve (S50% = 14 g) suggested catch value would be improved by 5–10%, or $100,000 to $200,000. The harvest strategy evaluations showed that greater benefits, in the order of 30–60% increases in the tiger annual catch value, could have been obtained by closing the fishery early in the year when annual effort levels were high (i.e., > 10,000 boat-days). In recent years, as effort levels have declined (i.e., ~4000 boat-days annually), expected benefits from such closures are more modest. In essence, temporal closures offer greater benefit when fishing mortality rates are high. A spatial analysis of Brown Tiger Prawn catch and effort was also undertaken to obtain a better understanding of the prawn population dynamics. This indicated that, to improve profitability of the fishery, fishers could consider closing the fishery in the period from June to October, which is already a period of low profitability. This would protect the Brown Tiger Prawn spawning stock, increase catch rates of all species in the lucrative pre-Christmas period (November–December), and provide fishers with time to do vessel maintenance, arrange markets for the next season’s harvest, and, if they wish, work at other jobs. The analysis found that the instantaneous rate of total mortality (Z) for the March–June period did not vary significantly over the last two decades. As the Brown Tiger Prawn population in Moreton Bay has clearly increased over this time period, an interesting conclusion is that the instantaneous rate of natural mortality (M) must have increased, suggesting that tiger prawn natural mortality may be density-dependent at this time of year. Mortality rates of tiger prawns for June–October were found to have decreased over the last two decades, which has probably had a positive effect on spawning stocks in the October–November spawning period. Abiotic effects on the prawns The influence of air temperature, rainfall, freshwater flow, the southern oscillation index (SOI) and lunar phase on the catch rates of the four main prawn species were investigated. The analyses were based on over 200,000 daily logbook catch records over 23 years (i.e., 1988–2010). Freshwater flow was more influential than rainfall and SOI, and of the various sources of flow, the Brisbane River has the greatest volume and influence on Moreton Bay prawn catches. A number of time-lags were also considered. Flow in the preceding month prior to catch (i.e., 30 days prior, Logflow1_30) and two months prior (31–60 days prior, Logflow31_60) had strong positive effects on Banana Prawn catch rates. Average air temperature in the preceding 4-6 months (Temp121_180) also had a large positive effect on Banana Prawn catch rates. Flow in the month immediately preceding catch (Logflow1_30) had a strong positive influence on Greasyback Prawn catch rates. Air temperature in the preceding two months prior to catch (Temp1_60) had a large positive effect on Brown Tiger Prawn catch rates. No obvious or marked effects were detected for Eastern King Prawns, although interestingly, catch rates declined with increasing air temperature 4–6 months prior to catch. As most Eastern King Prawn catches in Moreton Bay occur in October to December, the results suggest catch rates decline with increasing winter temperatures. In most cases, the prawn catch rates declined with the waxing lunar phase (high luminance/full moon), and increased with the waning moon (low luminance/new moon). The SOI explains little additional variation in prawn catch rates (~ <2%), although its influence was higher for Banana Prawns. Extrapolating findings of the analyses to long-term climate change effects should be interpreted with caution. That said, the results are consistent with likely increases in abundance in the region for the two tropical species, Banana Prawns and Brown Tiger Prawns, as coastal temperatures rise. Conversely, declines in abundance could be expected for the two temperate species, Greasyback and Eastern King Prawns. Corporate management structures An examination of alternative governance systems was requested by the industry at one of the early meetings, particularly systems that may give them greater autonomy in decision making as well as help improve the marketing of their product. Consequently, a review of alternative management systems was undertaken, with a particular focus on the potential for self-management of small fisheries (small in terms of number of participants) and corporate management. The review looks at systems that have been implemented or proposed for other small fisheries internationally, with a particular focus on self-management as well as the potential benefits and challenges for corporate management. This review also highlighted particular opportunities for the Moreton Bay prawn fishery. Corporate management differs from other co-management and even self-management arrangements in that ‘ownership’ of the fishery is devolved to a company in which fishers and government are shareholders. The company manages the fishery as well as coordinates marketing to ensure that the best prices are received and that the catch taken meets the demands of the market. Coordinated harvesting will also result in increased profits, which are returned to fishers in the form of dividends. Corporate management offers many of the potential benefits of an individual quota system without formally implementing such a system. A corporate management model offers an advantage over a self-management model in that it can coordinate both marketing and management to take advantage of this unique geographical advantage. For such a system to be successful, the fishery needs to be relatively small and self- contained. Small in this sense is in terms of number of operators. The Moreton Bay prawn fishery satisfies these key conditions for a successful self-management and potentially corporate management system. The fishery is small both in terms of number of participants and geography. Unlike other fisheries that have progressed down the self-management route, the key market for the product from the Moreton Bay fishery is right at its doorstep. Corporate management also presents a number of challenges. First, it will require changes in the way fishers operate. In particular, the decision on when to fish and what to catch will be taken away from the individual and decided by the collective. Problems will develop if individuals do not join the corporation but continue to fish and market their own product separately. While this may seem an attractive option to fishers who believe they can do better independently, this is likely to be just a short- term advantage with an overall long-run cost to themselves as well as the rest of the industry. There are also a number of other areas that need further consideration, particularly in relation to the allocation of shares, including who should be allocated shares (e.g. just boat owners or also some employed skippers). Similarly, how harvesting activity is to be allocated by the corporation to the fishers. These are largely issues that cannot be answered without substantial consultation with those likely to be affected, and these groups cannot give these issues serious consideration until the point at which they are likely to become a reality. Given the current structure and complexity of the fishery, it is unlikely that such a management structure will be feasible in the short term. However, the fishery is a prime candidate for such a model, and development of such a management structure in the future should be considered as an option for the longer term.

Thermal decomposition of hydrazinium aluminium sulfate hydrate and hydrazinate

As a part of our research programme on hydrazine derivatives [I-4]. we have prepared a number of hydrazinium metal sulfates [ 1.S] (N2 H5), M(SO4)2, where M = Mn, Fe, Co, Ni, Cu. Zn, Cd and Mg and their hydrazine adducts [2] of the type (N2H5)2M(SO4)2 . 3 N2H4. where M = Fe, Co and Ni, as well as N2H5AI(SO4)2 . 6N2H4. Recently, we reported [5.6] the thermal analysis of these compounds. Our .literature survey on the thermal analysis of alums [7] and aluminium salts [8] indicated that, although the preparation of hydrazinium aluminium sulfate dodecahydrate, N2H5Al(SO4)2 . 12 H2O, has been reported [9], there appears to be no report on its thermal analysis. Here, we report the results df the thermal analysis of N2H5Al(SO4)2 . 12 H2O and N2H5Al(SO4)2 . 2N2H4.

Quantum Chemical Studies of Intermolecular Interactions

This thesis studies the intermolecular interactions in (i) boron-nitrogen based systems for hydrogen splitting and storage, (ii) endohedral complexes, A@C60, and (iii) aurophilic dimers. We first present an introduction of intermolecular interactions. The theoretical background is then described. The research results are summarized in the following sections. In the boron-nitrogen systems, the electrostatic interaction is found to be the leading contribution, as 'Coulomb Pays for Heitler and London' (CHL). For the endohedral complex, the intermolecular interaction is formulated by a one-center expansion of the Coulomb operator 1/rab. For the aurophilic attraction between two C2v monomers, a London-type formula was derived by fully accounting for the anisotropy and point-group symmetry of the monomers.

Structure and Bonding in N-Methylacetamide Complexes of Alkali and Alkaline Earth Metals

A detailed crystallographic investigation of N-methylacetamide complexes of Li, Na, K, Mg and Ca has been made in view of its importance in the coordination chemistry and biochemistry of alkali and alkaline earth metals. The metal ions bind to the amide oxygen causing an increase in the carbonyl distance and a proportionate decrease in the central C-N bond distance. The decrease in the central C-N distance is accompanied by an increase in the distance of the adjacent C-C bond and a decrease in the adjacent C-N bond distance. The metal ion generally deviates from the direction of the lone pair of the carbonyl oxygen and also from the plane of the peptide, the out-of-plane deviation varying with the ionic potential of the cation. The metal-oxygen distance in alkali and alkaline earth metal complexes of a given coordination number also varies with the ionic potential of the cation, as does the strength of binding of the cations to the amide. The amide molecules are essentially planar in these complexes, as expected from the increased bond order of the central C-N bond. The NH bonds of the amide are generally hydrogen bonded to anions. The structures of the amide complexes are compared with those of other oxygen donor complexes of alkali and alkaline earth metals. The structural study described here also provides a basis for the interpretation of results from spectroscopic and theoretical investigations of the interaction of alkali and alkaline earth metal cations with amides.

Incomplete decomposition of alkali metal azides

The thermal decomposition of sodium azide has been studied in the temperature range 240–360°C in vacuum and under pressure of an inert gas, argon. The results show that the decomposition is partial 360°C. From the observations made in the present work, namely: (i) the decomposition is incomplete both under vacuum and inert gas; (ii) mass spectrometric studies do not reveal any decrease in the intensity of the background species, CO+2, CO+, H2O+, and (iii) sodium metal remains in the ‘free state’ as seen by the formation of a metallic mirror at temperatures above 300°C, it has been argued that the partial nature of decompostion is due to the confinement of the decomposition to intermosaic regions within the lattice.

Electron Spectroscopic Studies of Oxygen and Carbon Dioxide Adsorbed on Metal Surfaces

Adsorption of oxygen on Ni, Cu, Pd, Ag, and Au surfaces has been investigated by employing UV and X-ray photoelectron spectrscopy as well as electron energy loss spectroscopy (EELS). Molecularly chemisorbed (singlet) oxygen is found on Ni, Cu, Ag, and Au surfaces showing features such as stabilization of the rB* orbital, destabilization of the .nu orbital, higher O(1s) binding energy than the atomic species, and a band 2-3 eV below the Fermi level due to metal d-O(2p)u* interaction. 0-0 and metal-oxygen stretching frequencies have been observed in EELS. Physical adsorption of O2 is found to occur on Pd and Ni surfaces, only at high exposures in the latter case. Physical adsorption and multilayer condensation of CO, on metal surfaces are distinguished by characteristic relaxation shifts in UPS as well as O(1s) binding energies. Adsorption of CO on a Ni surface covered with presorbed atomic oxygen gives rise to C02.

Complexes of lanthanide iodides with 4-methylpyridine-1-oxide and 2-methylpyridine-1-oxide

Complexes of lanthanide iodides with 4-methylpyridine-1-oxide and 2-methylpyridine-1-oxide of the formulae Ln(4-MePyO)8I3.xH2O (x=0 or 2) and Ln(2-MePyO)5I3.xH2O (x=0, 1 or 3) have been prepared and characterized by analyses, conductance, infrared and proton NMR data. Infrared spectra of the complexes indicate that the coordination of the ligand to the metal ion takes place through the oxygen of the N-O group of the ligand. Proton NMR data for the paramagnetic complexes indicate that both contact and pseudocontact interactions are responsible for the isotropic shifts. Proton NMR spectra of the 2-methylpyridine-1-oxide complexes indicate a restricted rotation of the ligand about the N-O group.

Complexes of lanthanide perchlorates with N,N,N′,N′-tetramethyl-α-carboxamido-O-anisamide and N,N′-di-t-butyl-α-carboxamido-O-anisamide

A survey of the literature on lanthanide coordination compounds reveals that ligands involving ether oxygens as donor atoms have received very little attention [ 11. Only recently have the complexes of lanthanides with cyclic polyethers been characterized [l-3]. We report in this communication that interaction of rareearth perchlorates with two new ligands namely N,N,N’,N’-tetramethyl-u-carboxamido-Oanisamide (TMCA) and N,N’-di-t-butyl-crcarboxamido- 0-anisamide (DTBCA). The two ligands are potentially tridentate possessing two amide moieties and an ether linkage in between. The isolated complexes have been characterized by analysis, electrolytic conductance, infrared and electronic spectra. The ‘H and “C NMR spectra for the diamagnetic La3+ and Y3+ complexes are also discussed.

Photocytotoxic Oxovanadium(IV) Complexes Showing Light-Induced DNA and Protein Cleavage Activity

Oxovanadium(IV) complexes [VO(L)(B)]Cl-2 (1-3), where L is bis(2-benzimidazolylmethyl)amine and B is 1,10-phenanthroline(phen),dipyrido[3,2-d:2',3'-f]quinoxaline(dpq) or dipyrido[3,2-a:2',3'-c]phenazine (dppz), have been prepared, characterized, and their photo-induced DNA and protein cleavage activity studied. The photocytotoxicity of complex 3 has been studied using adenocarcinoma A549 cells, The phen complex 1, structurally characterized by single-crystal X-ray crystallography, shows the presence of a vanadyl group in six-coordinate VON5 coordination geometry. The ligands L and phen display tridentate and bidentate N-donor chelating binding modes, respectively. The complexes exhibit a d-d band near 740 nm in 15% DMF-Tris-HCl buffer (pH 7.2). The phen and dpq complexes display an irreversible cathodic cyclic voltammetric response near -0.8 V in 20% DMF-Tris-HCl buffer having 0.1 M KCl as supporting electrolyte. The dppz complex 3 exhibits a quasi-reversible voltammogram near -0.6 V (vs SCE) that is assignable to the V(IV)-V(III)couple. The complexes bind to calf thymus DNA giving binding constant values in the range of 6.6 x 10(4)-2.9 x 10(5) M-1. The binding site size, thermal melting and viscosity binding data suggest DNA surface and/or groove binding nature of the complexes. The complexes show poor ``chemical nuclease'' activity in dark in the presence of 3-mercaptopropionic acid or hydrogen peroxide. The dpq and dppz complexes are efficient photocleavers of plasmid DNA in UV-A light of 365 nm via a mechanistic pathway that involves formation of both singlet oxygen and hydroxyl radicals. The complexes show significant photocleavage of DNA in near-IR light (>750 nm) via hydroxyl radical pathway. Among the three complexes, the dppz complex 3 shows significant BSA and lysozyme protein cleavage activity in UV-A light of 365 nm via hydroxyl radical pathway. The dppz complex 3 also exhibits photocytotoxicity in non-small cell lung carcinoma/human lung adenocarcinoma A549 cells giving IC50 value of 17 mu M in visible light(IC50 = 175 mu M in dark).

Rotational isomerism about the Ca-CO bond in proline derivatives. 1H and 13C NMR studies of benzyloxycarbonyl-Pro-N-methylamide and pivaloyl-Pro-N-methylamide

The 270 MHz 1H n.m.r. spectrum of benzyloxycarbonyl-Pro-N-methylamide in CDCl3 is exchange broadened at 293° K. Spectral lines due to two species are frozen out at 253° K and a dynamically averaged spectrum is obtained at 323° K. A selective broadening of the Cβ and Cγ resonances in the 13C n.m.r. spectrum is observed at 253° K, with a splitting of the Cβ and Cγ resonances into a pair of lines of unequal intensity. A similar broadening of Cβ and Cγ peaks is also detected in pivaloyl-Pro-N-methylamide where cis-trans interconversion about the imide bond is precluded by the bulky t-butyl group. The rate process is thus attributed to rotation about the Cα-CO bond (ψ) and a barrier (ΔG#) of 14kcal mol-1 is estimated. 13C n.m.r. data for pivaloyl-Pro-N-methylamide in a number of solvents is presented and the differences in the Cβ and Cγ chemical shifts are interpreted in terms of rotational isomerism about the Cα-CO bond.

Magnetic behaviour in metal-organic frameworks-Some recent examples

The article describes the synthesis, structure and magnetic investigations of a series of metal-organic framework compounds formed with Mn+2 and Ni+2 ions. The structures, determined using the single crystal X-ray diffraction, indicated that the structures possess two- and three-dimensional structures with magnetically active dimers, tetramers, chains, two-dimensional layers connected by polycarboxylic acids. These compounds provide good examples for the investigations of magnetic behaviour. Magnetic studies have been carried out using SQUID magnetometer in the range of 2-300 K and the behaviour indicates a predominant anti-ferromagnetic interactions, which appears to differ based on the M-O-C-O-M and/or the M-O-M (M = metal ions) linkages. Thus, compounds with carboxylate (Mn-O-C-O-Mn) connected ones, [C3N2H [Mn(H2O)''C6H3(COO)(3)''], I, [''Mn(H2O (3)''aEuroeC(12)H(8)O(COO)(2)'']center dot H2O, II, [''Mn(H2O)''aEuroeC(12)H(8)O(COO)(2)''], III, show simple anti-ferromagnetic behaviour. The compounds with Mn-O/OH-Mn connected dimer and tetramer units in [NaMn''C6H3(COO)(3)''], IV, [Mn-2(A mu(3)-OH) (H2O)(2)''C6H3(COO)(3)'']center dot 2H(2)O, V, show canted-antiferromagnetic and anti-ferromagnetic behaviour, respectively. The presence of infinite one-dimensional -Ni-OH-Ni- chains in the compound, [Ni-2(H2O)(A mu(3)-OH)(2)(C8H5NO4], VI, gives rise to ferromagnet-like behaviour at low temperatures. The compounds, [Mn-3''C6H3(COO)(3)''(2)], VII and [''Mn(OH)''(2)''C12H8O(COO)(2)''], VIII, have two-dimensional infinite -Mn-O/OH-Mn- layers with triangular magnetic lattices, which resemble the Kagome and brucite-like layer. The magnetic studies indicated canted-antiferromagnetic behaviour in both the cases. Variable temperature EPR and theoretical magnetic modelling studies have been carried out on selected compounds to probe the nature of the magnetic species and their interactions with them.

Electrochemical properties and intermediate-temperature fuel cell performance of dense yttrium-doped barium zirconate with calcium addition

Although BaZr 0.8Y 0.2O 3-δ(BZY) possesses large bulk proton conductivity and excellent chemical stability, its poor sinterability and grain boundaries block proton conduction. In this work, the effect of Ca as a co-dopant and as a sintering aid (as CaO), on the sinterability, proton conductivity, and fuel cell performance of BZY was investigated. The addition of 4 mol% CaO significantly improved the BZY sinterability: BZY pellets with densities of 92.7% and 97.5% with respect to the theoretical density were obtained after sintering at 1500°C and 1600°C, respectively. The improved BZY sinterability by CaO addition resulted also in a large proton conductivity; at 600°C, the total conductivity of BZY-CaO was 2.14 × 10 -3 S/cm, in wet Ar. Anode-supported fuel cells with 25 μm-thick BZY-CaO electrolyte membranes were fabricated by a dual-layer co-firing technique. The peak power density of the fuel cell with a BZY-Ni/BZY-4CaO/BZY-LSCF (La 0.6Sr 0.4Fe 0.8Co 0.2O 3-δ) configuration was 141 mW/cm 2 at 700°C, several times larger than the reported values of BZY electrolyte membrane fuel cells sintered with the addition of CuO or ZnO, demonstrating promising features for practical fuel cell applications.

Peptide-lanthanide interactions. Crystal structure of a europium(III)-triglycine complex

Crystals of Eu-(Gly-Gly-Gly).(H2O)5.(ClO4)3 are triclinic, spacegroup P1BAR with a = 9.123 (2), b = 11.185 (5), c = 11.426 (2) angstrom; alpha = 90.79 (2), beta = 98.08 (1), gamma = 98.57 (2)-degrees; Z = 2. The europium cation is surrounded by four oxygens from three different peptide units and four oxygens from water molecules. The geometry around the metal is a distorted bi-capped trigonal prism. The peptide backbone conformation in this complex is compared with those in the free peptide and in various metal complexes. Considerable differences are observed between Eu(III) and Ca(II) complexes of triglycine. (C) Munksgaard 1994.

Dimethyl sulphoxide and dimethyl formamide complexes of Mn(III) perchlorate

Dimethyl sulphoxide (DMSO) and dimethyl formamide (DMF) complexes of Mn(III) perchlorate have been prepared and their conductivity, magnetic susceptibility and i.r. and electronic spectra studied. The complexes behave as uni-trivalent electrolytes in acetonitrile. Their magnetic moments of 5·1 B.M. show them to be of high spin type. Infra-red spectra show that oxygen is the donor atom in both complexes. The spin allowed electronic transition for d4 system, around 20,000 cm−1, ascribable to the 5Eg → 5T2g transition, suggests an octahedral configuration for these complexes