Synthesis of silica films at the air/water interface: Effect of template chain length and ionic strength

We have grown surfactant-templated silicate films at the air-water interface using n-alkyltrimethylammonium bromide and chloride in an acid synthesis with tetraethyl orthosilicate as the silicate source. The films have been grown with and without added salt (sodium chloride, sodium bromide) and with n-alkyl chain lengths from 12 to 18, the growth process being monitored by X-ray reflectometry. Glassy, hexagonal, and lamellar structures have been produced in ways that are predictable from the pure surfactant-water phase diagrams. The synthesis appears to proceed initially through an induction period characterized by the accumulation of silica-coated spherical micelles near the surface. All syntheses, except those involving C(12)TACl, show a sudden transformation of the spherical micellar phase to a hexagonal phase. This occurs when the gradually increasing ionic strength and/or changing ethanol concentration is sufficient to change the position of boundaries within the phase diagram. A possible mechanism for this to occur may be to induce a sphere to rod transition in the micellar structure. This transformation, as predicted from the surfactant-water phase diagram, can be induced by addition of salts and is slower for chloride than bromide counteranions. The hexagonal materials change in cell dimension as the chain length is changed in a way consistent with theoretical model predictions. All the materials have sufficiently flexible silica frameworks that phase interconversion is observed both from glassy to hexagonal and from hexagonal, to lamellar and vice versa in those surfactant systems where multiple phases are found to exist.

Synthesis and complexes of the sexidentate macrocycle 15-methyl-1,4,7,10,13-pentaazacyclohexadecan-15-amine

The potentially sexidentate polyamine macrocycle 15-methyl-1,4,7,10,13-pentaazacyclohexadecan-15-amine (1) was prepared via a copper(II)-templated route from 3,6,9-triazaundecan-1,ll-diamine, formaldehyde and nitroethane which first formed the copper(II) complex of the macrocycle 15-methyl-15-nitro-1,4,7,10,13-pentaazacyclohexadecane (2), reduced subsequently with zinc and aqueous acid to yield 1. The hexaamine 1, with five secondary amine groups in the macrocyclic ring and one pendant primary amine group, forms inert sexidentate octahedral complexes with cobalt(III), chromium(III) and iron(III). An X-ray structure of [Co(1)](ClO4)(3) defines the distorted octahedron of the complex cation and shows it is a symmetrical isomer with all nitrogens bound and the central aza group trans to the pendant primary amine group. The [M(1)](3+) ions are all stable indefinitely in aqueous solution and exhibit spectra consistent with MN6 d(3) (Cr), low-spin d(5) (Fe) and low-spin d(6) (Co) electronic ground states. For each complex, a reversible M(III/II) redox couple is observed. (C) 2000 Elsevier Science S.A. All rights reserved.

Decoherence and coherent population transfer between two coupled systems

We show that an arbitrary system described by two dipole moments exhibits coherent superpositions of internal states that can be completely decoupled fi om the dissipative interactions (responsible for decoherence) and an external driving laser field. These superpositions, known as dark or trapping states, can he completely stable or can coherently interact with the remaining states. We examine the master equation describing the dissipative evolution of the system and identify conditions for population trapping and also classify processes that can transfer the population to these undriven and nondecaying states. It is shown that coherent transfers are possible only if the two systems are nonidentical, that is the transitions have different frequencies and/or decay rates. in particular, we find that the trapping conditions can involve both coherent and dissipative interactions, and depending on the energy level structure of the system, the population can be trapped in a linear superposition of two or more bare states, a dressed state corresponding to an eigenstate of the system plus external fields or, in some cases. in one of the excited states of the system. A comprehensive analysis is presented of the different processes that are responsible for population trapping, and we illustrate these ideas with three examples of two coupled systems: single V- and Lambda-type three-level atoms and two nonidentical tao-level atoms, which are known to exhibit dark states. We show that the effect of population trapping does not necessarily require decoupling of the antisymmetric superposition from the dissipative interactions. We also find that the vacuum-induced coherent coupling between the systems could be easily observed in Lambda-type atoms. Our analysis of the population trapping in two nonidentical atoms shows that the atoms can be driven into a maximally entangled state which is completely decoupled from the dissipative interaction.

Synthesis and structure elucidation of kappa-casein (45-87) - A two dimensional nuclear magnetic resonance study

We have shown that 44 amino acid residues N-terminal segment of kappa-casein exhibits considerable a-helical structure. This prompted us to investigate the structures of the remaining segments of kappa-casein. Thus, in this study the chemical synthesis and structure elucidation of the peptide 45-87 amino acid residues of kappa-casein is reported. The peptide was assembled using solid phase peptide synthesis methodology on pam resin, cleaved via HF, freeze dried and, after purification, characterised by mass spectrometry (observed m/z 4929; calculated mit 4929.83). The amino acid sequence of the peptide is: CKPVALINNQFLPYPYYAKPAAVRSPAQILQWQVLSNTVPAKA Its structure elucidation has been carried out using circular dichroism (CD) and nuclear magnetic resonance (NMR) techniques. CD spectrum of the peptide shows it to be a random structure in water but in 30% trifluoroethanol the peptide exhibits considerable structure. The 1D and 2D NMR spectra corroborated the results of CD. The structure elucidation of the peptide using TOCSY and NOESY NMR techniques will be discussed.

Conotoxin TVIIA, a novel peptide from the venom of Conus tulipa - 1. Isolation, characterization and chemical synthesis

A novel conotoxin belonging to the 'four-loop' structural class has been isolated from the venom of the piscivorous cone snail Conus tulipa. It was identified using a chemical-directed strategy based largely on mass spectrometric techniques. The new toxin, conotoxin TVIIA, consists of 30 amino-acid residues and contains three disulfide bonds. The amino-acid sequence was determined by Edman analysis as SCSGRDSRCOOVCCMGLMCSRGKCVSIYGE where O = 4-transl-hydroxyproline. Two under-hydroxylated analogues, [Pro10]TVIIA and [Pro10,11]TVIIA, were also identified in the venom of C. tulipa. The sequences of TVIIA and [Pro10]TVIIA were further verified by chemical synthesis and coelution studies with native material. Conotoxin TVIIA has a six cysteine/four-loop structural framework common to many peptides from Conus venoms including the omega-, delta- and kappa-conotoxins. However, TVIIA displays little sequence homology with these well-characterized pharmacological classes of peptides, but displays striking sequence homology with conotoxin GS, a peptide from Conus geographus that blocks skeletal muscle sodium channels. These new toxins and GS share several biochemical features and represent a distinct subgroup of the four-loop conotoxins.

Metal-directed synthesis routes to a 16-membered tetraazamacrocycle with two pendant primary amine groups

The reaction of the bis(propane-1,3-diamine)copper(II) ion with paraformaldehyde and nitroethane in dry methanol under basic conditions produces a macrocyclic product, (cis-3,11-dimethyl-3,11-dinitro-1,5,9,13-tetraazacyclohexadecane)copper(II) perchlorate, in low yield, compared with the good yield obtained in the parallel chemistry possible even under aqueous conditions using palladium(II) as a template. The palladium complex was reduced with zinc amalgam in dilute aqueous acid to yield the metal-free 16-membered macrocyclic hexaamine, in this case re-complexed and characterised by an X-ray crystal structure as the (cis-3,11-dimethyl-1,5,9,13-tetraazacyclohexadecane-3,11-diamine)copper(II) perchlorate. The copper ion is found in a tetragonally elongated and trigonally-distorted octahedral environment, with all six of the ligand nitrogens coordinated, the two primary amine pendant groups occupying cis sites. (C) 2000 Elsevier Science S.A. All rights reserved.

Screening for abdominal aortic aneurysm: lessons from a population-based study

Objectives: To test the acceptability of screening and to identify modifiable risk factors for abdominal aortic aneurysm (AAA) in men. Design: A trial of ultrasound screening for AAA in a population-based random sample of men aged 65-83 years, and a cross-sectional case-control comparison of men in the same sample. Participants: 12203 men who had an ultrasound examination of their abdominal aorta, and completed a questionnaire covering demographic, behavioural and medical factors. Main outcome measures: Prevalence of AAA, and independent associations of AAA with demographic, medical and lifestyle factors. Results: Invitations to screening produced a corrected response of 70.5%. The prevalence of AAAs (> 30 mm) rose from 4.8% in men aged 65-69 years to 10.8% in those aged 80-83 years. The overall prevalence of large (> 50 mm) aneurysms was 0.69%. In a multivariate logistic model Mediterranean-born men had a 40% lower risk of AAA (> 30 mm) compared with men born in Australia (odds ratio [OR], 0.6; 95% CI, 0.4-0.8), while ex-smokers had a significantly increased risk of AAA (OR, 2.3; 95% CI, 1.9-2.8), and current smokers had even higher risks. AAA was significantly associated with established coronary and peripheral arterial disease and a waist:hip ratio greater than 0.9; men who regularly undertook vigorous exercise had a lower risk (OR, 0.8; 95% CI, 0.7-1.0). Conclusion: Ultrasound screening for AAA is acceptable to men in the likely target population. AAA shares some but not all of the risk factors for occlusive vascular disease, but the scope for primary prevention of AAA in later life is limited.

Dental set-vice provision in private general practice for an insured population in New South Wales, Australia

Objective To determine patterns of dental set-vices provided to a cohort of the insured population 18 years and over, in private general practice in New South Wales, Australia. Basic research design A cohort study using the person-years method and Poisson regression for analysis. Setting Data were derived from claims records submitted by members of a health insurance fund (Government Employees Health Fund-GEHF) for rebates during the study period 1 January 1992-31 December 1995. Participants There were 133,467 members aged 18 years and over from New South Wales. Main outcome measures To determine, by age group, for those members who used private general practice and made a claim (referred to as 'patients') the annual number of visits, total number of services received per year and number of services received at a visit, Results The mean number of visits per patient was 2.4 per year with patients under 45 years making fewer visits than the 45-54 age group reference category. Mean number of services utilised per patient-year was 5.9, with services provided increasing from 3.5 for the 18-24-year-old group, reaching a plateau of approximately 6.2 for those aged 45 years or more. The number of services received per visit was 2.4 and there were no differences by age. Service mix was dominated by restorative (35%), diagnostic (27%), and preventive services (18%); with age specific variations observed. Conclusions Age was found to be an important determinant in the use of dental services, independent of membership duration and gender.

Review of "Comorbidity, disability and the need for treatment for DSM-IV psychiatric disorders in an insured population"

Background: This study presents estimates of 12 month and current prevalences of DSM-IV disorders, and the related comor-bidity, disability and service utilization, derived from a national probability sample in Australia. Methods: The DSM-IV psychiatric disorders among persons aged 18 and over in the Australian population were assessed with data collected by lay interviewers using the Composite International Diagnostic Interview, other screening interviews and measures of disability and service utilization. The response rate was 78.1% and the final sample size was 10,641 adults. Results: Close to 20% reported at least one twelve month disorder and 13% a disorder current within the past 30 days. ICD-10 diagnoses were also derived, DSM-IV was the more conservative classification whether or not the new clinical significance criteria was applied. Major depression, any personality disorder, and alcohol dependence were the three most common twelve month disorders, generalized anxiety disorder replaced alcohol dependence as the third most common current disorder. The sexes has similar rates of any disorder, but women had higher rates of affective and anxiety disorders, men higher rates of substance use disorders. Prevalence of most disorders declined with age and education, and were lower among those employed or married. Respondents whose symptoms met criteria for three or more disorders in the past year had greatly increased rates of disability and of mental health consultations. The affective and somatoform disorders were associated with the highest rates of disability. Only 36% of people with a mental disorder this year had consulted for a mental problem, and most had seen a general practitioner. We identified those with a current disorder who were disabled or multiply comorbid - only half had consulted and of those who had not, more than half said they did not need treatment. Conclusions: The 12 month prevalence was lower than reported in the US National Comorbidity Survey but method factors might account for this. The relationships between prevalence and demographic variables, and between comorbidity, disability and service utilization were similar to those found in the US survey. Australia has a national health insurance scheme with total coverage and access to medical help is available to all, commonly at little or no cost. We identify the high rate of not consulting among those with a current disorder, and additional disability or multiple comorbidity, as an important public health problem. Kessler argued for more research on barriers to professional help seeking. This report reinforces his conclusion and shows that economic barriers are not the dominant issue.

Hormonal factors and risk of aneurysmal subarachnoid hemorrhage - An international population-based, case-control study

Background and Purpose-Subarachnoid hemorrhage (SAH) is more common in women than in men, but the role of hormonal factors in its etiology remains uncertain. The aim of this study was to examine the relationship between hormonal factors and risk of SAH in women. Methods-This was a prospective, multicenter, population-based, case-control study performed in 4 major urban centers in Australia and New Zealand. Two hundred sixty-eight female cases of first-ever aneurysmal SAH occurred during 1995-1998. Controls were 286 frequency-matched women from the general population of each center. Outcome measures included risk of SAH associated with use of oral contraceptive pills (OCPs), hormone replacement therapy (HRT), and various endogenous hormonal factors including menstrual patterns, parity, age at birth of first child, and breast-feeding practices. Results-Cases and controls did not differ with regard to menstrual and reproductive history except in age at bir th of first child, where older age was associated with reduced risk of SAH (odds ratio [OR], 0.63; 95% CI, 0.43, 0.91). Relative to never use of HRT, the adjusted OR for over use of HRT was 0.64 (95% CI, 0.41, 0.98), which did not alter significantly after further adjustment for possible confounding factors. Borderline evidence of an inverse association was detected for past use of HRT (adjusted OR, 0.59; 95% CI, 0.30, 1.13) and current use of HRT (adjusted OR, 0.67; 95% CI, 0.40, 1.13), but there was no evidence of an association for use of OCPs (adjusted OR, 0.97; 95% CI, 0.58, 1.60). Conclusions-The risks of SAH are lower in women whose first pregnancy is at an older age and women who have ever used HRT but not OCPs. The findings suggest an independent etiologic role for hormonal factors in the pathogenesis of aneurysmal SAH and provide support for a protective role fur HRT on risk of SAH in postmenopausal women.