Molecular Lego (R): non-centrosymmetric alignment within interdigitating layers

(E)-N-Hexadecyl-4-[2-(4-octadecyloxynaphthyl) ethenyl] quinolinium bromide, which has a wide-bodied chromophore and terminal n-alkyl groups, adopts a U-shape when spread at the air-water interface but a stretched conformation when compressed to ca. 35 mN m(-1). The high-pressure phase has a narrow stability range prior to collapse but may be extended from 40 to 60 mN m(-1) by co-spreading the dye in a 1 : 1 ratio with docosanoic acid. The mixed Langmuir-Blodgett (LB) film has a monolayer thickness of 4.6 +/- 0.2 nm which decreases to 2.5 +/- 0.1 nm layer(-1) in the bulk, the reduction arising from an interdigitating layer arrangement, both top and bottom. It is the first example of LB-Lego(R) and, in addition, represents the only fully interdigitating structure with non-centrosymmetrically aligned chromophores. They are tilted 38 degrees from the substrate normal. The second-harmonic intensity increases quadratically with the number of layers, i.e. as I-(N)(2 omega) = (I(1)N2)-N-2 omega, with a second-order susceptibility of chi ((2))(zzz) = 30 pm V-1 at 1064 nm for refractive indices of n(omega) = 1.55 and n(2 omega) = 1.73, d = 2.5 nm layer(-1) and phi = 38 degrees. Angle resolved X-ray photoelectron spectra (XPS) of these films provide no evidence of the bromide counterion, which suggests that it is replaced by OH 2 or HCO3-, which occur naturally in the aqueous subphase, or C21H43COO- from the co-deposited fatty acid. This probably applies to all cationic dyes deposited by the LB technique.

Historical PCDD Inputs and Their Source Implications from Dated Sediment Cores in Queensland (Australia)

Recent investigations have demonstrated the presence of an unidentified source of polychlorinated dibenzo-p-dioxins (PCDDs) in the coastal zone of Queensland (Australia). The present study provides new information on the possible PCDD sources and their temporal input to this environment. Two estuarine sediment cores were collected in northern Queensland for which radiochemical chronologies were established. Core sections from different depositional ages, up to three centuries, have been analyzed for 2,3,7,8-substituted PCDDs and polychlorinated dibenzofurans (PCDFs). Variations of PCDD concentrations in the sediment cores over several centuries of depositional history were relatively small, and elevated PCDD levels were still present in sediment slices from the early 17th century. PCDD/F isomer patterns and congener profiles in sediments deposited during the last 350 years were almost identical and correlated well to the characteristic profiles observed in surface sediments and soils from the entire Queensland coastline. Profiles were dominated by higher chlorinated PCDDs, in particular octachlorodibenzodioxin (OCDD), whereas PCDF concentrations were below or near the limit of detection. These results indicate the presence of a PCDD source prior to industrialization and production of commercial organochlorine products. Further, the present study demonstrates that PCDD input patterns have been similar along an extensive but localized area over at least several centuries, contributing relatively high concentrations of PCDDs to the coastal system of Queensland.

Smoke derived from burnt vegetation stimulates germination of arable weeds

A commercially available smoke-water solution (Seed Starter (R)) stimulated the germination of caryopses and intact florets of Avena fatua L. The solution was most effective when diluted (5-50%) and presented to intact or dehulled grain that had received a short period of dry after-ripening. It was less effective when applied at full strength or to grains that had been freshly harvested. The same stimulatory effect was observed in par-fly after-ripened caryopses of nine different wild oat biotypes obtained from three different cropping regions of the world. When freshly harvested caryopses were re-tested with the commercial solution (100%) for just 7 days prior to placement on to distilled water, a much higher germination percentage was possible than seen with continuous smoke-water incubation. The stimulatory ability of smoke water was more closely matched to that of gibberellic acid than to potassium nitrate, which had little or no effect on freshly harvested caryopses. The smoke-water solution (5-100%) was tested on the germination of 18 other cool temperate arable weed species. All monocotyledonous species tested (viz. Avena sterilis ssp. ludoviciana L., Alopecurus myosuroides, Sorghum halepense, Phalaris paradoxa) responded positively, while those of the dicotyledonous species were either strongly stimulated (greater than or equal to 40% stimulation Malva neglecta), moderately stimulated (greater than or equal to 20% stimulation Galium aparine, Veronica persica), slightly stimulated (Polygonum persicaria, P pennsylvanicum, Fallopia convolvulus), unaffected (P. aviculare, Sinapis arvensis, Heracleum sphondylium, Angelica sylvestris, Mercurialis annua, Veronica hederifolia) or inhibited (Lamium purpureum). The optimal concentrations required to stimulate germination of the monocotyledonous species were similar to those observed for A. fatua (5-10%). However, for the dicotyledonous species slightly stronger solutions were required (10-20%). When the unaffected species were retested using a 10-day pre-chilling treatment, smoke water showed a small promotive response in three (S. arvensis, P. aviculare and V hederifolia) of the six species. When four different smoke-water solutions (Seed Starter (R), Regen 2000 (R), charred-wood solution and wheat-straw solution) were tested on two representative species (A. fatua and M. neglecta), three formulations were effective in promoting the germination of both species, while the fourth (charred-wood solution) was only active on A. fatua. The active concentrations were different for the four solutions. Three solutions were active in the 2-20% dilution range, while the fourth (Regen 2000 (R)) was only active in the 1-2% dilution range and was inhibitory at higher concentrations. These observations are discussed in the context that smoke may play an important ecological role in the management and control of introduced weeds in native and arable communities.

FAM deubiquitylating enzyme is essential for preimplantation mouse embryo development

FAM is a developmentally regulated substrate-specific deubiquitylating enzyme. It binds the cell adhesion and signalling molecules beta -catenin and A-F-6 in vitro, and stabilises both in mammalian cell culture. To determine if FAM is required at the earliest stages of mouse development we examined its expression and function in preimplantation mouse embryos. FAM is expressed at all stages of preimplantation development from ovulation to implantation. Exposure of two-cell embryos to FAM-specific antisense, but not sense, oligodeoxynucleotides resulted in depletion of the FAM protein and failure Of the embryos to develop to blastocysts. Loss of FAM had two physiological effects, namely, a decrease in cleavage rate and an inhibition of cell adhesive events. Depletion of FAM protein was mirrored by a loss of beta -catenin such that very little of either protein remained following 72 h culture. The residual beta -catenin was localised to sites of cell-cell contact suggesting that the cytoplasmic pool of beta -catenin is stabilised by FAM. Although AF-6 levels initially decreased they returned to normal. However, the nascent protein was mislocalised at the apical surface of blastomeres. Therefore FAM is required for preimplantation mouse embryo development and regulates beta -catenin and AF-6 in vivo. (C) 2001 Elsevier Science Ireland Lid. All rights reserved.

The pharmacokinetics of once-daily dosing of ceftriaxone in critically ill patients

The aim of this study was to determine the pharmacokinetic profile of the normal recommended dose of ceftriaxone in critically ill patients and to establish whether the current daily dosing recommendation maintains plasma concentrations adequate for antibacterial efficacy. Ceftriaxone at a recommended dose of 2 g iv was administered od to 12 critically ill patients with severe sepsis and normal serum creatinine concentrations. Blood samples were taken at predetermined intervals over the first 24 h and on day 3 for measurement of ceftriaxone concentrations. There was wide variability in drug disposition, explained by the presence of variable renal function and identified by the measurement of creatinine clearance. In nine patients with normal renal function, there was a high level of creatinine clearance(mean +/- S.D., 41 +/- 12 mL/min) and volume of distribution (20 +/- 3.3 L), which resulted in an elimination half-life of 6.4 +/- 1.1 h. In comparison with normal subjects, ceftriaxone clearance was increased 100%, volume of distribution increased 90% and the elimination half-life was similar. Three patients had substantially suboptimal plasma ceftriaxone concentrations. We confirm previous findings that ceftriaxone clearance in critically ill patients correlates with renal clearance by glomerular filtration. The elimination half-life is prolonged (21.4 +/- 9.8 h) in critically ill patients with renal failure when compared with previously published data in non-critically ill patients with renal failure. We conclude that in critically ill patients with normal renal function, inadequate plasma concentrations may result following od bolus dosing of ceftriaxone. Drug accumulation may occur in critically ill patients with renal failure.

Do generalized visual training programmes for sport really work? An experimental investigation

We assessed the effectiveness of two generalized visual training programmes in enhancing visual and motor performance for racquet sports. Forty young participants were assigned equally to groups undertaking visual training using Revien and Gabor's Sports Vision programme (Group 1), visual training using Revien's Eyerobics (Group 2), a placebo condition involving reading (Group 3) and a control condition involving physical practice only (Group 4). Measures of basic visual function and of sport-specific motor performance were obtained from all participants before and immediately after a 4-week training period. Significant pre- to post-training differences were evident on some of the measures; however, these were not group-dependent. Contrary to the claims made by proponents of generalized visual training, we found no evidence that the visual training programmes led to improvements in either vision or motor performance above and beyond those resulting simply from test familiarity.

Childhood neglect and cognitive development in extremely low birth weight infants: A prospective study

Objective. To examine the relationship between child maltreatment and cognitive development in extremely low birth weight infants, adjusting for perinatal and parental risk factors. Methods. A total of 352 infants with birth weight of

The Role of Non-Market Valuation in Forest Management and Recreation Policy

Forests, and particularly those where native and mixed species are gown, provide a variety of non-wood values, important among which are recreation and environmental services. Substantial progress has been made in recent years in estimating economic values on these services. A considerable amount of research on forest values has been carried out recently in tropical and sub-tropical eastern Australia, some of which is reported in the following papers. The need for estimates of non-wood forest benefits is apparent, and it is clear that further development of techniques and a greater understanding of the way these values can be integrated into public-sector decision making is required.

A survey of dental and oral trauma in south-east Queensland during 1998

Background: This project investigated the aetiology of dental and oral trauma in a population in southeast Queensland. The literature shows there is a lack of dental trauma studies which are representative of the general Australian population. Method: Twelve suburbs in the south-east district of Queensland were randomly selected according to population density in these suburbs for each 25th percentile. All dental clinics in these suburbs were eligible to participate. Patients presenting with dental and oral trauma were eligible to participate. Results: A total of 197 patients presented with dental/oral trauma over a 12 month period. The age of patients ranged from 1-64 years whilst the most frequently presenting age group was 6-10 years. There was a total of 363 injured teeth with an average of 1.8 injured teeth per patient. Males significantly outnumbered females in the incidence of trauma. Conclusions: The highest frequency of trauma occurred in the 6-10 year age group. Most injuries in this group occurred while playing or riding bicycles. In the next most prevalent trauma group, 16-20 years, trauma occurred as a result of fighting and playing sport. Overall, males significantly outnumbered females by approximately 1.8:1.0. The majority of injuries in the deciduous dentition were to periodontal tissues. In the secondary dentition most injuries were to hard dental tissue and pulp.

[18O]-Oxygen incorporation reveals novel pathways in spiroacetal biosynthesis by Bactrocera cacuminata and B. cucumis

The origins of the oxygen atoms in 1,7-dioxaspiro[5.5]undecane (1) and hydroxyspiroacetal (2) from Bactrocera cacuminata, and in 2,8-dimethyl-1,7-dioxaspiro[5.5]undecane (3) and hydroxyspiroacetal (4) from B. cucumis, have been investigated by incorporation studies from both [18O2]-dioxygen and [18O]-water. Combined GC-MS examination and high-field NMR analysis have demonstrated that all oxygen atoms in 1 and 2 from B. cacuminata are dioxygen derived, but in contrast, the spiroacetals 3 and 4 from B. cucumis incorporate one ring oxygen from water and one ring oxygen (and the hydroxyl oxygen in 4) from [18O2]-dioxygen. These results reveal not only the generality of monoxygenase mediation of spiroacetal formation in Bactrocera sp., but also an unexpected complexity in their biosynthesis. A general paradigm accommodating these and other observations is presented.

An XPS study of an isomorphous trivalent lanthanoid series

X-ray photoelectron spectroscopy has been used to investigate the core electron binding energies within an isomorphous series of lanthanoid complexes; [LnL(1)] where Ln=La-Lu (except Pm) and H3L is the heptadentate ligand 2,2',2-tris(salicylideneimino)triethylamine. This study also examines spin-orbit coupling of the trivalent lanthanoids bound to this organic ligand and addresses the issue of satellite peaks in the spectra. (C) 2002 Elsevier Science B.V. All rights reserved.

Monooxygenase stereoselectivity in the biosynthesis of stereoisomeric spiroacetals in the cucumber fly, Bactrocera cucumis

The stereoselectivity of hydroxylation of alkyltetrahydropyran-2-ols (or their biological equivalents) in the formation of stereoisomers of 2,8-dimethyl-1,7-dioxaspiro[5.5]undecanes in male Bactrocera cucumis has been investigated. Racemic, (6R)-, and (6S)-6-methyl-2-[5-H-2(1)]-n-pentyltetrahydropyran-2-ol was administered under an [O-18(2)]-enriched atmosphere. The stereochemistry and isotopic composition of generated spiroacetals were monitored by combined enantioselective GC-MS. The monooxygenase(s) strongly prefers the (6S)-substrate and furnishes predominantly the (S)-alcohol and then the (2S,6R,8S)-2,8-dimethyl-1,7-dioxaspiro[5.5]undecane. The (2S,6S,8R) and (2R,6S,8S) (E,Z)-isomers appear to be derived in vivo predominantly from (R)-hydroxylation of the (6S)-tetrahydropyranol.

Empirical evidence for ultrametric structure in multi-layer perceptron error surfaces

Combinatorial optimization problems share an interesting property with spin glass systems in that their state spaces can exhibit ultrametric structure. We use sampling methods to analyse the error surfaces of feedforward multi-layer perceptron neural networks learning encoder problems. The third order statistics of these points of attraction are examined and found to be arranged in a highly ultrametric way. This is a unique result for a finite, continuous parameter space. The implications of this result are discussed.

PrrC from Rhodobacter sphaeroides, a homologue of eukaryotic Sco proteins, is a copper-binding protein and may have a thiol-disulfide oxidoreductase activity

PrrC from Rhodobacter sphaeroides provides the signal input to a two-component signal transduction system that senses changes in oxygen tension and regulates expression of genes involved in photosynthesis (Eraso, J.M. and Kaplan, S. (2000) Biochemistry, 39, 2052-2062; Oh, J.-I. and Kaplan, S. (2000) EMBO J. 19, 42374247). It is also a homologue of eukaryotic Sco proteins and each has a C-x-x-x-C-P sequence. In mitochondrial Sco proteins these cysteines appear to be essential for the biogenesis Of the Cu-A centre of respiratory cytochrome oxidase. Overexpression and purification of a water-soluble and monomeric form of PrrC has provided sufficient material for a chemical and spectroscopic study of the properties of the four cysteine residues of PrrC, and its ability to bind divalent cations, including copper. PrrC expressed in the cytoplasm of Escherichia coli binds Ni2+ tightly and the data are consistent with a mononuclear metal site. Following removal of Ni2+ and formation of renatured metal-free rPrrC (apo-PrrC), Cu2+ could be loaded into the reduced form of PrrC to generate a protein with a distinctive UV-visible spectrum, having absorbance with a lambda(max) of 360 nm. The copper:PrrC ratio is consistent with the presence of a mononuclear metal centre. The cysteines of metal-free PrrC oxidise in the presence of air to form two intramolecular disulfide bonds, with one pair being extremely reactive. The cysteine thiols with extreme O-2 sensitivity are involved in copper binding in reduced PrrC since the same copper-loaded protein could not be generated using oxidised PrrC. Thus, it appears that PrrC, and probably Sco proteins in general, could have both a thiol-disulfide oxidoreductase function and a copper-binding role. (C) 2002 Published by Elsevier Science B.V. on behalf of the Federation of European Biochemical Societies.