Intra- vs intermolecular photoinduced electron transfer reactions of a macrocyclic donor-acceptor dyad

The synthesis, structural characterization, and photophysical behavior of a 14-membered tetraazamacrocycle with pendant 4-dimethylaminobenzyl (DMAB) and 9-anthracenylmethyl groups is reported (L-3, 6-((9-anthracenylmethyl)amino)-trans-6,13-dimethyl-13-((4-dimethylaminobenzyl)amino)-1,4,8,11-tetraaza-cyclotetradecane). In its free base form, this compound displays rapid intramolecular photoinduced electron transfer (PET) quenching of the anthracene emission, with both the secondary amines and the DMAB group capable of acting as electron donors. When complexed with Zn(II), the characteristic fluorescence of the anthracene chromophore is restored as the former of these pathways is deactivated by coordination. Importantly, it is shown that the DMAB group, which remains uncoordinated and PET active, acts only very weakly to quench emission, by comparison to the behavior of a model Zn complex lacking the pendant DMAB group, [ZnL2](2+) (Chart 1). By contrast, Stern-Volmer analysis of intermolecular quenching of [ZnL2](2+) by N,N-dimethylaniline (DMA) has shown that this reaction is diffusion limited. Hence, the pivotal role of the bridge in influencing intramolecular PET is highlighted.

Complexes of cytotoxic chelators from the dipyridyl ketone isonicotinoyl hydrazone (HPKIH) analogues

In an effort to better understand the antiproliferative effects of the tridentate hydrazone chelators di-2-pyridyl ketone isonicotinoyl hydrazone (HPKIH) and di-2-pyridyl ketone benzoyl hydrazone (HPKBH), we report the coordination chemistry of these ligands with the divalent metal ions, Mn, Co, Ni, Cu, and Zn. These complexes are compared with their Fe-II analogues which were reported previously. The crystal structures of Co(PKIH)(2), Ni(PKIH)(2), Cu(PKIH)(2), Mn(PKBH)(2), Ni(PKBH)(2), Cu(PKBH)(2), and Zn(PKBH)(2) are reported where similar bis-tridenate coordination modes of the ligands are defined. In pure DMF, all complexes except the Zn-II compounds exhibit metal-centered M-III/II (Mn, Fe, Co, Ni) or M-II/I (Cu) redox processes. All complexes show ligand-centered reductions at low potential. Electrochemistry in a mixed water/DMF solvent only elicited metal-centered responses from the Co and Fe complexes. Remarkably, all complexes show antiproliferative activity against the SK-N-MC neuroepithelioma cell line similar to (HPKIH) or significantly greater than that of the (HPKBH) ligand which suggests a mechanism that does not only involve the redox activity of these complexes. In fact, we suggest that the complexes act as lipophilic transport shuttles that allow entrance to the cell and enable the delivery of both the ligand and metal which act in concert to inhibit proliferation.

Interaction of zinc(II) with the cyclic octapeptides, cyclo[Ile(Oxn)-D-Val(Thz)](2) and ascidiacyclamide, a cyclic peptide from Lissoclinum patella

The interactions between zinc salts and the naturally occurring cyclic octapeptide ascidiacyclamide in methanol, as well as a synthetic analogue cyclo[Ile(Oxn)-D-Val(Thz)](2), were monitored by H-1 NMR and CD spectroscopy. Three zinc complexes were identified, their relative amounts depending on the nature of the anion (perchlorate, triflate or chloride) and the presence or absence of base. Binding constants for two of the zinc species were calculated from CD or H-1 NMR spectra, [Zn(L - H)](+) (KZn(L-H) = [Zn(L - H)(+)]/[Zn2+][(L - H)(-)] = 10(7 +/- 2) M-1; 95% methanol/5% water, 298.0 K, NEt3/HClO4 buffer 0.04 M) and [ZnLCl](+) (K-ZnCIL = [ZnCIL+]/[Zn2+][Cl-][L] = 10(7.2) (+/-) (0.1) M-2; d(3)-methanol, 301 K).

Dynamic Behavior of the Jahn-Teller distorted Cu(H2O)(6)(2+) ion in Cu2+ doped Cs-2[Zn(H2O)(6)](ZrF6)(2) and the crystal structure of the host lattice

The temperature dependence of the X- and Q-band EPR spectra of Cs-2[Zn(H2O)(6)](ZrF6)(2) containing similar to1% Cu2+ is reported. All three molecular g-values vary with temperature, and their behavior is interpreted using a model in which the potential surface of the Jahn-Teller distorted Cu(H2O)(6)(2+) ion is perturbed by an orthorhombic strain induced by interactions with the surrounding lattice. The strain parameters are significantly smaller than those reported previously for the Cu(H2O)(6)(2+) ion in similar lattices. The temperature dependence of the two higher g-values suggests that in the present compound the lattice interactions change slightly with temperature. The crystal structure of the Cs-2[Zn(H2O)(6)](ZrF6)(2) host is reported, and the geometry of the Zn(H2O)(6)(2+) ion is correlated with lattice strain parameters derived from the EPR spectrum of the guest Cu2+ complex.

High-level and phonological awareness abilities of children following management for supratentorial tumour: Part II

Background. Limited information is available regarding the impact of childhood tumour on the cerebral hemispheres and supratentorial cranial fossa. However, a recent study found that children managed for a tumour located in this region may demonstrate reduced general language abilities. However, the indirect or direct impact of a tumour in this region on higher-level language abilities in childhood is at present largely unknown. Materials and methods. The present study examined the higher language and phonological awareness abilities of five children treated for supratentorial tumour ranging in age from seven to fourteen years in age. Assessments included measures of receptive and expressive semantic abilities, inferencing, figurative language, and problem solving, as well as a comprehensive pre-literacy test. Results. As a group, reductions were evident in problem solving, and in the ability to receive and decode content of high-level language when compared to a group of age- and gender-matched peers. At an individual level, only two of five children managed for supratentorial tumour demonstrated language deficits. These two cases were noted to be the same children previously identified as also having general language deficits. More widespread findings were noted in phonological awareness, with four of the five children previously managed for supratentorial tumour demonstrating weaknesses in one or more areas. Conclusions. Findings demonstrated that weaknesses in general language ability in children managed for supratentorial tumour may indicate higher-level language difficulties. Language abilities beyond general measures of language should be monitored, as well as long-term consideration of phonological awareness abilities in this population.

Elevations, Goetz Residence II, Red Hill, Brisbane

Hand-drawn elevations of proposed residence.

Floor plan, Goetz Residence II, Red Hill, Brisbane

Hand-drawn plan of proposed residence.

Substrate-inhibited kinetics with catalyst deactivation in an isothermal CSTR. II. Multiple pseudosteady states and reactor failure

Analytical expressions are derived for the time and magnitude of failure of an isothermal CSTR with substrate-inhibited kinetics, caused by slow catalyst deactivation under three types of parallel and series mechanisms. Reactors operating at high space velocity are found to be most susceptible to early failure and poisoning by product is more dangerous than by reactant. The magnitude of the jump across steady states depends solely on the Langmuir-Hinshelwood kinetic parameters and a detailed analysis of reactor behavior during the jump itself is given.

Chemical treatment of Escherichia coli. II. Direct extraction of recombinant protein from cytoplasmic inclusion bodies in intact cells

A method is presented for the direct extraction of the recombinant protein Long-R-3-IGF-I from inclusion bodies located in the cytoplasm of intact Escherichia coli cells. Chemical treatment with 6M urea, 3 mM EDTA, and 20 mM dithiothreitol (DTT) at pH 9.0 proved an effective combination for extracting recombinant protein from intact cells. Comparable levels of Long-R-3-IGF-I were recovered by direct extraction as achieved by in vitro dissolution following mechanical disruption. However, the purity of directly extracted recombinant protein was lower due to contamination by bacterial cell components. The kinetics of direct extraction are described using a first-order equation with the time constant of 3 min. Urea appears important for permeabilization of the cell and dissolution of the inclusion body. Conversely, EDTA is involved in permeabilization of the cell wall and DTT enhances protein release. pH proved to be important with lower levels of protein release achieved at low pH values (

Matrix elements of U(2n) generators in a multishell spin-orbit basis. II. The two-shell nonzero shift ACCs and U(2n) generator MEs

This is the second in a series of articles whose ultimate goal is the evaluation of the matrix elements (MEs) of the U(2n) generators in a multishell spin-orbit basis. This extends the existing unitary group approach to spin-dependent configuration interaction (CI) and many-body perturbation theory calculations on molecules to systems where there is a natural partitioning of the electronic orbital space. As a necessary preliminary to obtaining the U(2n) generator MEs in a multishell spin-orbit basis, we must obtain a complete set of adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis. The zero-shift coefficients were obtained in the first article of the series. in this article, we evaluate the nonzero shift adjoint coupling coefficients for the two-shell composite Gelfand-Paldus basis. We then demonstrate that the one-shell versions of these coefficients may be obtained by taking the Gelfand-Tsetlin limit of the two-shell formulas. These coefficients,together with the zero-shift types, then enable us to write down formulas for the U(2n) generator matrix elements in a two-shell spin-orbit basis. Ultimately, the results of the series may be used to determine the many-electron density matrices for a partitioned system. (C) 1998 John Wiley & Sons, Inc.

Improving wheat simulation capabilities in Australia from a cropping systems perspective - II. Testing simulation capabilities of wheat growth

To simulate cropping systems, crop models must not only give reliable predictions of yield across a wide range of environmental conditions, they must also quantify water and nutrient use well, so that the status of the soil at maturity is a good representation of the starting conditions for the next cropping sequence. To assess the suitability for this task a range of crop models, currently used in Australia, were tested. The models differed in their design objectives, complexity and structure and were (i) tested on diverse, independent data sets from a wide range of environments and (ii) model components were further evaluated with one detailed data set from a semi-arid environment. All models were coded into the cropping systems shell APSIM, which provides a common soil water and nitrogen balance. Crop development was input, thus differences between simulations were caused entirely by difference in simulating crop growth. Under nitrogen non-limiting conditions between 73 and 85% of the observed kernel yield variation across environments was explained by the models. This ranged from 51 to 77% under varying nitrogen supply. Water and nitrogen effects on leaf area index were predicted poorly by all models resulting in erroneous predictions of dry matter accumulation and water use. When measured light interception was used as input, most models improved in their prediction of dry matter and yield. This test highlighted a range of compensating errors in all modelling approaches. Time course and final amount of water extraction was simulated well by two models, while others left up to 25% of potentially available soil water in the profile. Kernel nitrogen percentage was predicted poorly by all models due to its sensitivity to small dry matter changes. Yield and dry matter could be estimated adequately for a range of environmental conditions using the general concepts of radiation use efficiency and transpiration efficiency. However, leaf area and kernel nitrogen dynamics need to be improved to achieve better estimates of water and nitrogen use if such models are to be use to evaluate cropping systems. (C) 1998 Elsevier Science B.V.

Copper(II) complexes of mono- and di-nucleating hexaamines

The potentially hexadentate polyamines N,N,N',N'-tetrakis(2-aminoethyl)ethane-1,2-diamine (L-1) and the octamethylated analogue N,N,N',N'-tetrakis(2-dimethylaminoethyl)ethane 1,2-diamine (L-2) have been complexed with copper(II) and the crystal structures of their complexes determined. A trigonal-bipyramidal co-ordination geometry for [Cu(HL1)][ClO4](3) was found where one aminoethyl arm is not co-ordinated. By contrast, a dinuclear structure of formula [(H2O)Cu(L-2)Cu(OH)](3+) was determined for the N-methylated analogue, where the hexaamine acts as a bridging ligand between the two square-pyramidal metal centres. Electronic and EPR spectroscopy are both consistent with these structures being maintained in solution.

A novel tricopper(II) complex of a polyamine alcohol

The trinuclear copper(II) complex of a new polyamino alcohol ligand has been isolated; it exhibits a structure similar to that found at the active site of ascorbate oxidase.

Young children, adolescents and alcohol - Part II: Reputation enhancement and self-concept

The research reported builds on our earlier work (Houghton, Carroll, & Odgers, 1998) which explored young children's and adolescents' views pertaining to knowledge and awareness of alcohol and alcohol-related issues. In this second study 640 (286 male and 354 female) school students randomly selected from five primary schools and five high schools in Perth, Western Australia participated. Data were obtained using The Which Group picture booklet questionnaire which comprises five parts and utilises illustrations (drawn by a professional children's artist) to gather information about children's and adolescents' orientations towards alcohol risk social situations, reputation enhancement, self-concept, and other related issues. Of the sample, 73% of males and 70.6% of females had tried alcohol, with beer being consumed most often. Significantly more participants in higher Year levels had tried alcohol. Over 90% said they drank at a party. Multivariate analysis revealed that nine of the 11 dependent variables contributed to the significant main effect of alcohol risk group, of which three were self-concept variables and six were reputation enhancement variables. It appears that individuals with the highest levels of orientation to alcohol risk believe that they are liked by their families, are physically attractive and have greater confidence in themselves. They also have higher levels of Admiration of Alcohol Related Activities and also of prosocial activities. While striving to attain a non-conforming reputation these individuals also wish to be ideally perceived by others as conforming. Gender and Age differences are investigated.