Synthesis and structural properties of Anhydrous Rare Earth Cinnamates, [RE(cinn)3]

Anhydrous rare earth tris(cinnamates) [RE(cinn)3] (RE = La–Lu, Y and Sc and cinnH = trans-cinnamic acid) were prepared by metathesis in water and by direct reaction of the metal with cinnamic acid in a 1,2,4,5-tetramethylbenzene flux at ca. 200 °C. X-ray crystal structure determinations and X-ray powder data show that, in the solid state, the larger lanthanoids (La–Dy) form an isomorphous polymeric series consisting of homoleptic nine-coordinate metal centres bonded to three chelating and bridging tridentate cinnamates. The late REIII cinnamate (RE = Dy, Ho–Lu, Y) complexes also form linear one-dimensional polymeric chains with all RE metal atoms being seven-coordinate. The cinnamates are either bound tridentate bridging in a μ-η2:η1 fashion, or μ-η1:η1syn-syn bidentate bridging. A structural break occurs at dysprosium which has been characterised in both crystallographic forms, and gives solely the late RE form when precipitated at 80 °C. ScIII cinnamate was also isolated as an analytically pure precipitate which was, again, found to be anhydrous in nature. A structural change was identified by powder XRD between the late REIII cinnamates and ScIII cinnamate.

Recent developments in corrosion inhibitors based on rare earth metal compounds

Rare earth organic compounds can provide an environmentally safe and non-toxic alternative to chromates as corrosion inhibitors for some steel and aluminium applications. For steel lanthanum 4-hydroxy cinnamate offers corrosion protection and reduces the susceptibility to hydrogen embrittlement. Recent work has also indicated that it inhibits the corrosion of steel in environments containing high levels of carbon dioxide. For aluminium alloys, cerium diphenyl phosphate provides excellent corrosion inhibition in chloride environments, and reduces susceptibly to stress corrosion cracking. Furthermore, for both steel and aluminium alloys filiform corrosion can be suppressed when rare earth inhibitor compounds are added as pigments to polymer coatings. The levels of inhibition observed are thought to be due to synergistic effects between the rare earth and organic parts of these novel compounds, and are related to the various species that may be present in the complex chemical conditions that develop in solution close to a metal surface. This paper reviews some of the published research conducted by the group at Deakin University over recent years.©2014 Institute of Materials, Minerals and Mining.

Rare earth 4-hydroxycinnamate compounds as carbon dioxide corrosion inhibitors for steel in sodium chloride solution

A series of rare earth 4-hydroxycinnamate compounds including Ce(4OHCin)3, La(4OHCin)3, and Pr(4OHCin)3 has been synthesized and evaluated as novel inhibitors for carbon dioxide corrosion of steel in CO2-saturated sodium chloride solutions. Electrochemical measurements and surface analysis have shown that these REM(4OHCin)3 compounds effectively inhibited CO2 corrosion by forming protective inhibiting deposits that shut down the active electrochemical corrosion sites on the steel surface. Inhibition efficiency was found to increase in the order Ce(4OHCin)3 < La(4OHCin)3 < Pr(4OHCin)3 and with increase in inhibitor concentration up to 0.63 mM. Detailed insights into corrosion inhibition mechanism of these compounds in carbon dioxide environment are also provided.

Feltability of cashmere and other rare animal fibres and the effects of nutrition and blending with wool on cashmere feltability

Felting is a unique attribute of animal fibres used for the production of a range of industrial and apparel textiles. Felting can be an adverse attribute as a consequence of dimensional shrinkage during laundering. As there is little objective information regarding the feltability of rare animal fibres or the factors which may affect felting three investigations were undertaken. A survey (n = 114) of the feltability of cashmere from different origins of production, cashgora, quivet, camel hair, llama, guanaco, bison wool, cow fibre and yak wool quantified the large variation between and within these fibre types. Cashmere from some origins and cashgora produced higher feltball density than the other fibres. Different nutritional management of cashmere goats (n = 35) showed that cashmere grown by poorly fed goats had a lower propensity to felt compared with cashmere grown by better fed goats. A consequence of the progressive blending of cashmere (n = 27) with a low propensity to felt superfine wool (high fibre curvature) increased the propensity of the blend to felt, but when the same cashmere was blended with low curvature superfine wool, there was little or no effect on feltability. The mechanisms which lead to variance in feltability of these fibres were quantified with multiple regression modelling. The mechanisms were similar to those reported for wools, namely variations in the resistance to compression, fibre curvature and mean fibre diameter, with likely effects of fibre crimp form. It is possible to source cashmere and other animal fibres which have different propensities to felt and therefore to produce textiles which are likely to have different textile properties.

The influence of rare earth mercaptoacetate on the initiation of corrosion on AA2024-T3 Part II: The influence of intermetallic compositions within heavily attacked sites

Localised corrosion is typical on AA2024-T3 due to intermetallic particles embedded in the alloy. The effect of intermetallic compositions on corrosion are not yet fully understood. EPMA data on AA2024-T3 surfaces before and after a 16. min immersion, analyses the influence of intermetallic clustering on the severity attack at local sites. While sites with a high number of domains and a large S-phase surface area typically lead to severe attack, maximising these features did not always lead to severe corrosion attack. Cerium or praseodymium mercaptoacetate inhibited corrosion ring formation. The common trends observed from such attack sites was also discussed.

Accepting risk in the acceleration of drug development for rare cancers.

Rare cancers collectively contribute a disproportionate fraction of the total burden of cancer. The oncology community is increasingly facing small numbers of patients with each cancer subtype, requiring cooperation and collaboration to complete multicentre trials that advance knowledge and patient care. At the same time, new insights into the biology of rare cancers have led to an explosion in knowledge and development of targeted agents. These insights and techniques are set to revolutionise the care of patients with cancer. However, drug development strategies and the availability of new agents for rare cancers are at risk of stalling owing to the ever-increasing complexity and costs of clinical trials. Finding solutions to these problems is imperative to the future of cancer care. We propose that a greater degree of risk sharing is needed than is currently accepted to enable the use of new methods with confidence, and to keep pace with scientific advancement.

Investigation of corrosion inhibition mechanisms of rare-earth mercaptoacetate inhibitors on AA2024-T3

 Corrosion inhibition mechanisms on the aerospace alloy, AA2024-T3, was investigated for the inhibitor combination of rare earth metals and mercaptoacetate. The inhibitor demonstrated synergistic protection for AA2024-T3 from localised corrosion. It is intended to be a more environmentally friendly alternative to toxic chromate-based inhibitors.

The influence of rare earth mercaptoacetate on the initiation of corrosion on AA2024-T3 Part I: average statistics of each intermetallic composition

De-alloying of S-phase in AA2024-T3 in the presence chlorides, is well-known. However, it is unclear how rare earth mercaptoacetate inhibitors affect this process when immersed in a 0.1. M NaCl solution. This paper analyses data obtained using EPMA on AA2024-T3 surfaces before and after a 16. min immersion period. Cerium and praseodymium mercaptoacetate inhibited the de-alloying process of S-phase particles. Although no significant change in composition was observed for cathodic intermetallics, each appeared to participate in local corrosion reactions as evidenced by the development of surface oxides. Clustering between S-phase and one of the Cu-containing intermetallic domains was also evident.

Rare earth 3-(4′-hydroxyphenyl)propionate complexes

The reaction of lanthanoid chlorides or nitrates with sodium 3-(4′-hydroxyphenyl)propionate (Na4hpp) in methanol or water has yielded complexes [La4(4hpp)12(H2O)6]·4H2O·MeOH (1), [Ce2(4hpp)6(H2O)3]·(H2O)·2.5(EtOH) (2a) (after crystallization from ethanol), [Ho(4hpp)3(H2O)2] (5), [Er(4hpp)3(H2O)2]·1.5(H2O) (6), and [Lu(4hpp)3]·H2O crystal composition (7), as well as heterobimetallics [NaCe2(4hpp)7(H2O)2]·3(H2O) (2b), [NaPr2(4hpp)7(H2O)2]·3(H2O) (3), and [NaNd2(4hpp)7(H2O)(MeOH)]·(H2O)·3(MeOH) (4). The structures of homometallic complexes 1, 2a, 6, and 7 reveal one-dimensional coordination polymers and vividly illustrate the effect of lanthanoid contraction with a decline in coordination numbers in the series from 9-11 (1), 9,10 (2a), 8 (6) to 7 (7) through variations in carboxylate coordination and ligation of water. Bimetallic complexes 2a and 4 each exhibit five different carboxylate binding modes as well as coordination of the 4-OH substituent of 4hpp to sodium thereby linking 1D polymer chains into a 2D network with both 9 and 10 coordinate Ln atoms and 6 coordinate sodium. Bulk products after drying lose solvent of crystallization in some cases (2a, 6), or exchange MeOH for water (4). X-ray powder diffraction indicates that bulk 2b and 3 are isotypic, as are bulk 5 and 6. In contrast to the excellent corrosion protection of lanthanum 4-hydroxycinnamate, compound 1 is ineffective in preventing the corrosion of mild steel, thereby establishing the importance of the -CHCH- structural unit of the former in its anti-corrosion properties. However the flexible -CH2-CH2- chain of the 4hpp ligand enables the crystal engineering of its lanthanoid complexes in a wide variety of structures as well as effective crystallization for structure determination, whereas the analogous 4-hydroxycinnamates have so far evaded structural characterization except for Ln = La, Ce owing to crystallization problems.