Future work in rural Southland

The New Zealand Kellogg Rural Leaders Programme develops emerging agribusiness leaders to help shape the future of New Zealand agribusiness and rural affairs. Lincoln University has been involved with this leaders programme since 1979 when it was launched with a grant from the Kellogg Foundation, USA.Southland is a rich farming area. It has a reliable climate, fertile soils and a variety of topography. Its cool winters help to keep pests and diseases at bay. While New Zealand itself is renowned as a very favoured farming country, Southland produces well above national average yields in all its established products. Therefore it can be expected that our economy will continue to be overwhelmingly reliant on our established pastoral and cropping industries. This report is focused mainly on opportunities to increase variety and quality of life in rural Southland

A coordinatively flexible hexadentate ligand gives structurally isomeric complexes M-2(L)X-3 (M = Cu, Zn; X = Br, Cl)

Polypyridyl multidentate ligands based on ethylenediamine backbones are important metal-binding agents with applications in biomimetics and homogeneous catalysis. The seemingly hexadentate tpena ligand [systematic name: N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetate] reacts with zinc chloride and zinc bromide to form trichlorido[mu-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dizinc(II), [Zn-2(C22H24N5O2)Cl-3], and tribromido[mu-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dizinc(II), [Zn2Br3(C22H24N5O2)]. One Zn-II ion shows the anticipated N5O coordination in an irregular six-coordinate site and is linked by an anti carboxylate bridge to a tetrahedral ZnX3 (X = Cl or Br) unit. In contrast, the Cu-II ions in aquatribromido[mu-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dicopper(II)-tribromido[mu-N,N,N'-tris(pyridin-2-ylmethyl)ethylenediamine-N'-acetato]dicopper(II)-water (1/1/6.5) [Cu2Br3(C22H24N5O2)][Cu2Br3(C22H24N5O2)(H2O)]center dot 6.5H(2)O, occupy two tpena-chelated sites, one a trigonal bipyramidal N3Cl2 site and the other a square-planar N2OCl site. In all three cases, electrospray ionization mass spectra were dominated by a misleading ion assignable to [M(tpena)](+) (M = Zn2+ and Cu2+)

Reduction of hypervalent iodine by coordination to iron(iii) and the crystal structures of PhIO and PhIO₂

Iodine L3-edge XANES spectra using reference compounds with formal iodine oxidation states spanning −1 to +7 show that iodine in an Fe(iii) coordinated iodosylbenzene (PhIO) is reduced compared to parent hypervalent PhIO which has been structurally characterized.</p

cis Donor Influence on O-O Bond Lability in Iron(III) Hydroperoxo Complexes:Oxidation Catalysis and Ligand Transformation

The Fe-III/Fe-II redox potentials for [Fe(tpen)](2+/3+), [Fe-(tpena)](+/2+), and [Fe (tpenO)](+/2+) (N-R-N,N',N'-tris (2-pyridylmethyl)ethane-1,2-diamine, where R = CH2C6H4N, CH2COO-, CH2CH2O-, respectively) span 470 mV with the oxidation potentials following the order [Fe-II(tpenO)](+) (MeOH) &lt;[Fe-II(tpena)](+) (MeCN) &lt;[Fe-II(tpen)](2+) (MeCN). In their +3 oxidation states the complexes react with 1 equiv of H2O2 to give the purple [Fe-III(OOH)(HL)](n+) (n = 2 for L = tpena, tpenO; n = 3 for L = tpen). A pyridine arm is decoordinated in these complexes, furnishing a second coordination sphere base which is protonated at ambient pH. The lifetimes of these transient species depend on how readily the substrate (sometimes the solvent) is oxidized and reflect the trend in both the O-O bond lability and oxidizing potency of the putative iron-based oxidant derived from the iron(III) peroxides. In methanol solution, [Fe-III(tpenO)](2+) and [Fe-III(tpena)](2+) exist in their Fe(III) states and hence the formation of [Fe-III(OOH)(Htpena)](2+) and [Fe-III(OOH)(HtpenO)(2+) is instantaneous. This is in contrast to the short lag time that occurs before adduct formation between [Fe-II(tpen)](2+) and H2O2 due to the requisite prior oxidation of the solution-state iron(II) complex to its iron(III) state. Stabilization of the +3 iron oxidation state in the resting state catalysts affords complexes that activate H2O2 more readily with the consequence of higher yields in the oxidation of the C-H bonds using H2O2 as terminal oxidant. The presence of a cis monodentate carboxylato donor increases the rate of oxidation by hydrogen atom transfer in comparison to the systems with an alkoxo or pyridine in this position. Competing with substrate oxidation is the oxidative modification of the alkoxido group in [Fe-III(tpenO)](2+), converting it to a carboxylato group in the presence of H2O2: in effect, transforming tpenO to tpena.</p

Trichlorido[(meth­yl{2-[meth­yl(2-pyridyl­meth­yl)amino]eth­yl}amino)acetonitrile]iron(III) methanol hemisolvate

The title compound, [FeCl3(C12H18N4)]·0.5CH3OH, contains an FeIII ion in a distorted octa­hedral coordination environment. The neutral N,N′,N′′-tridentate ligand adopts a fac coordination mode, and chloride ligands lie trans to each of the three coordinated N atoms. In the crystal, the complexes form columns extending parallel to the approximate local threefold axes of the FeN3Cl3 octa­hedra, and the columns are arranged so that the uncoordinated nitrile groups align in an anti­parallel manner and the pyridyl rings form offset face-to-face arrangements [inter­planar separations = 2.95 (1) and 3.11 (1) Å; centroid–centroid distances = 5.31 (1) and 4.92 (1) Å]. The methanol solvent mol­ecule is disordered about a twofold rotation axis

[N,N-Bis(2-pyridylmeth­yl)glycinato-κ4 N,N′,N′′,O]dichloridoiron(III)–[N,N-bis­(2-pyridylmeth­yl)glycine-κ4 N,N′,N′′,O]dichloridozinc(II) (1/1)

The title compound, [Fe(C14H14N3O2)Cl2]·[ZnCl2(C14H15N3O2)], is formulated as [FeIII(bpg)Cl2][ZnIICl2(bpgH)], where bpg is the tetra­dentate ligand N,N-bis­(2-pyridylmeth­yl)glycine. The structure contains one crystallographically distinct complex with FeIII and ZnII atoms present in a 50:50 ratio in a single-atom site. The non-coordinated O atoms of the carboxyl groups of bpg meet across crystallographic inversion centres, forming O—H⋯O hydrogen bonds that include only one H atom per two complexes, consistent with the 1:1 disorder of FeIII and ZnII

2-Carbamylpyridinium tetra­chlorido­ferrate(III)

The title compound, (C6H7N2O)[FeCl4], contains two carbamylpyridinium (picolinamidinium) cations, which are linked into chains by N+—H⋯O hydrogen bonds formed between protonated pyridyl N atoms and carbonyl groups. Tetra­chloridoferrate(III) anions lie between these chains, accepting N—H⋯Cl hydrogen bonds from both H atoms of the picolinamidium –NH2 group

(2,2′-Bipyridine-4,4′-dicarb­oxy­lic acid-κ2 N,N′)chlorido(2,2′:6′,2′′-terpyridyl-κ3 N,N′,N′′)ruthenium(II) perchlorate ethanol monosolvate monohydrate

In the title compound, [RuCl(C15H11N3)(C12H8N2O4)]ClO4·C2H5OH·H2O, the geometry of the ClN5 coordination set around the RuII atom is close to octa­hedral, but distorted on account of the limited bite angles of the polypyridyl ligands. The complexes are linked by O—H⋯O hydrogen bonds between the carboxyl groups and the crystal lattice water mol­ecules into chains along [110]. Face-to-face stacking inter­actions are formed between terpyridine ligands, with inter­planar separations of 3.66 (1) and 3.42 (1) Å, and between bipyridine-4,4′-dicarb­oxy­lic acid ligands, with inter­planar separations of 3.65 (1) and 3.72 (1) Å. Three O atoms of the perchlorate ion are each disordered equally over two positions. The hy­droxy group of the ethanol mol­ecule is also disordered over two sites with refined occupancies of 0.794 (9) and 0.206 (9)

Understanding breast cancer patients' preference for two types of exercise training during chemotherapy in an unblinded randomized controlled trial

<p>Abstract</p> <p>Background</p> <p>Patient preference for group assignment may affect outcomes in unblinded trials but few studies have attempted to understand such preferences. The purpose of the present study was to examine factors associated with breast cancer patients' preference for two types of exercise training during chemotherapy.</p> <p>Methods</p> <p>Breast cancer patients (N = 242) completed a battery of tests including a questionnaire that assessed patient preference and the theory of planned behavior (TPB) prior to being randomized to usual care, resistance exercise training (RET), or aerobic exercise training (AET).</p> <p>Results</p> <p>99 (40.9%) participants preferred RET, 88 (36.4%) preferred AET, and 55 (22.7%) reported no preference. Past exercisers (p = 0.023), smokers (p = 0.004), and aerobically fitter participants (p = 0.005) were more likely to prefer RET. As hypothesized, participants that preferred AET had more favorable TPB beliefs about AET whereas participants that preferred RET had more favorable TPB beliefs about RET. In multivariate modeling, patient preference for RET versus AET was explained (R²= .46; p < 0.001) by the difference in motivation for RET versus AET (β = .56; p < 0.001), smoking status (β = .13; p = 0.007), and aerobic fitness (β = .12; p = 0.018). Motivational difference between RET versus AET, in turn, was explained (R²= .48; p < 0.001) by differences in instrumental attitude (β = .27; p < 0.001), affective attitude (β = .25; p < 0.001), and perceived behavioral control (β = .24; p < 0.001).</p> <p>Conclusion</p> <p>Breast cancer patients' preference for RET versus AET during chemotherapy was predicted largely by a difference in motivation for each type of exercise which, in turn, was based on differences in their beliefs about the anticipated benefits, enjoyment, and difficulty of performing each type of exercise during chemotherapy. These findings may help explain patient preference effects in unblinded behavioral trials.</p> <p>Trial Registration</p> <p>ClinicalTrials.gov Identifier NCT00115713.</p