Extraction of cesium ions from aqueous solutions using calix[4]arene-bis(tert-octylbenzo-crown-6) in ionic liquids

Solvent extraction of cesium ions from aqueous solution to hydrophobic ionic liquids without the introduction of an organophilic anion in the aqueous phase was demonstrated using calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6) as an extractant. The selectivity of this extraction process toward cesium ions and the use of a sacrificial cation exchanger (NaBPh4) to control loss of imidazolium cation to the aqueous solutions by ion exchange have been investigated.

Small angle neutron scattering from 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids ([C(n)mim][PF6], n=4, 6, and 8)

The presence of local anisotropy in the bulk, isotropic, and ionic liquid phases-leading to local mesoscopic inhomogeneity-with nanoscale segregation and expanding nonpolar domains on increasing the length of the cation alkyl-substituents has been proposed on the basis of molecular dynamics (MD) simulations. However, there has been little conclusive experimental evidence for the existence of intermediate mesoscopic structure between the first/second shell correlations shown by neutron scattering on short chain length based materials and the mesophase structure of the long chain length ionic liquid crystals. Herein, small angle neutron scattering measurements have been performed on selectively H/D-isotopically substituted 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids with butyl, hexyl, and octyl substituents. The data show the unambiguous existence of a diffraction peak in the low-Q region for all three liquids which moves to longer distances (lower Q), sharpens, and increases in intensity with increasing length of the alkyl substituent. It is notable, however, that this peak occurs at lower values of Q (longer length scale) than predicted in any of the previously published MD simulations of ionic liquids, and that the magnitude of the scattering from this peak is comparable with that from the remainder of the amorphous ionic liquid. This strongly suggests that the peak arises from the second coordination shells of the ions along the vector of alkyl-chain substituents as a consequence of increasing the anisotropy of the cation, and that there is little or no long-range correlated nanostructure in these ionic liquids.

4-Amino-1,8-naphthalimide-based Tröger's bases as high affinity DNA targeting fluorescent supramolecular scaffolds

The synthesis and photophysical and biological investigation of fluorescent 1,8-naphthalimide conjugated Troger's bases 1-3 are described. These structures bind strongly to DNA in competitive media at pH 7.4, with concomitant modulation in their fluorescence emission. These structures also undergo rapid cellular uptake, being localized within the nucleus within a few hours, and are cytotoxic against HL60 and (chronic myeloid leukemia) K562 cell lines.

Modelling of the sodium complex of a calixarene tetraester in the 1,3-alternate conformation

This paper describes the use of molecular mechanics to model the geometry of the sodium complex of a calix[4] arene tetraester, in the 1,3-alternate conformation 1. Partial charges were assigned to the calixarene on the basis of semi-empirical (AM1, PM3, MNDO, INDO, CNDO and ZINDO) calculations and the binding of the sodium ion to the calixarene was modelled using molecular mechanics. Agreement between the optimised and X-ray structures of the complex was very good. The effect of placing the cation in different starting positions on the energy-minimised geometry of the complex is described.

Chemoenzymatic synthesis of chiral 4,4 '-bipyridyls and their metal-organic frameworks

The first enantiopure 4,4'-bipyridyls, 6, 8, and 9 have been prepared in four or five steps via bacterial dioxygenase-catalysed cis-dihydroxylation of 4-chloroquinoline 1 and C-C coupling; ligands 6 and 9 are found to be effective building blocks for the preparation of chiral metal-organic frameworks as demonstrated with the rational synthesis of two pillared-grid structures [Zn-2(fumarate)(2)(L)], which exhibit interesting structural and dynamic aspects.

Extreme ultraviolet emission lines of Ca XV in solar and laboratory spectra

New R-matrix calculations of electron impact excitation rates in Ca XV are used to derive theoretical electron density diagnostic emission line intensity ratios involving 2s(2)2p(2)- 2s2p(3) transitions, specifically R-1 = I(208.70 Angstrom)/I(200.98 Angstrom), R-2 = I(181.91 Angstrom)/I(200.98 Angstrom), and R-3 = I(215.38 Angstrom)/I(200.98 Angstrom), for a range of electron temperatures (T-e = 10(6.4)-10(6.8) K) and densities (Ne = 10(9)-10(13) cm(-3)) appropriate to solar coronal plasmas. Electron densities deduced from the observed values of R-1, R-2, and R-3 for several solar flares, measured from spectra obtained with the Naval Research Laboratory's S082A spectrograph on board Skylab, are found to be consistent. In addition, the derived electron densities are in excellent agreement with those determined from line ratios in Ca XVI, which is formed at a similar electron temperature to Ca XV. These results provide some experimental verification for the accuracy of the line ratio calculations, and hence the atomic data on which they are based. A set of eight theoretical Ca XV line ratios involving 2s(2)2p(2)-2s2p(3) transitions in the wavelength range similar to140-216 Angstrom are also found to be in good agreement with those measured from spectra of the TEXT tokamak plasma, for which the electron temperature and density have been independently determined. This provides additional support for the accuracy of the theoretical line ratios and atomic data.

Physicochemical and mineralogical characteristics of soil/saprolite cores from a field research site, Tennessee

Site characterization is an essential initial step in determining the feasibility of remedial alternatives at hazardous waste sites. Physicochemical and mineralogical characterization of U-contaminated soils in deeply weathered saprolite at Area 2 of the DOE Field Research Center (FRC) site, Oak Ridge, TN, was accomplished to examine the feasibility of bioremediation. Concentrations of U in soil–saprolite (up to 291 mg kg–1 in oxalate-extractable Uo) were closely related to low pH (ca. 4–5), high effective cation exchange capacity without Ca (64.7–83.2 cmolc kg–1), amorphous Mn content (up to 9910 mg kg–1), and the decreased presence of relative clay mineral contents in the bulk samples (i.e., illite 2.5–12 wt. %, average 32 wt. %). The pH of the fill material ranged from 7.0 to 10.5, whereas the pH of the saprolite ranged from 4.5 to 8. Uranium concentration was highest (about 300 mg kg–1) at around 6 m below land surface near the saprolite–fill interface. The pH of ground water at Area 2 tended to be between 6 and 7 with U concentrations of about 0.9 to 1.7 mg L–1. These site specific characteristics of Area 2, which has lower U and nitrate contamination levels and more neutral ground water pH compared with FRC Areas 1 and 3 (ca. 5.5 and

Perceived and reported access to the general practitioner: an international comparison of universal access and mixed private/public systems.

Timely and convenient access to primary healthcare is essential for the health of the population as delays can incur additional health and financial costs. Access to health care is under increasing scrutiny as part of the drive to contain escalating costs, while attempting to maintain equity in service provision. The objective was to compare primary care services in Republic of Ireland and Northern Ireland, and to report on perceived and reported access to GP services in universal access and mixed private/public systems. A questionnaire study was performed in Northern Ireland (NI) and the Republic of Ireland (ROI). Patients of 20 practices in the ROI and NI were contacted (n = 22,796). Main outcome measures were overall satisfaction and the access to GP services. Individual responses and scale scores were derived using the General Practice Assessment Questionnaire (G-PAQ). The response rate was 52% (n = 11,870). Overall satisfaction with GP practices was higher in ROI than in NI (84.2% and 80.9% respectively). Access scores were higher in ROI than in NI (69.2% and 57.0% respectively) Less than 1 in 10 patients in ROI waited two or more working days to see a doctor of choice (8.1%) compared to almost half (45.0%) in NI. In NI overall satisfaction decreased as practice size increased; 82.8%, 80.4%, and 75.8%. In both systems, in large practices, accessibility is reduced when compared to smaller practices. The faster access to GP services in ROI may be due to the deterrent effect of the consultation charge freeing up services although, as it is the poorest and sickest who are deterred by the charge this improved accessibility may come at a significant cost in terms of equity. The underlying concern for policy makers centres around provision of equitable services.

Effect of osteoporosis on bone mineral density and fracture repair in a rat femoral fracture model

Osteoporosis (OP) is one of the most prevalent bone diseases worldwide with bone fracture the major clinical consequence. The effect of OP on fracture repair is disputed and although it might be expected for fracture repair to be delayed in osteoporotic individuals, a definitive answer to this question still eludes us. The aim of this study was to clarify the effect of osteoporosis in a rodent fracture model. OP was induced in 3-month-old rats (n = 53) by ovariectomy (OVX) followed by an externally fixated, mid-diaphyseal femoral osteotomy at 6 months (OVX group). A further 40 animals underwent a fracture at 6 months (control group). Animals were sacrificed at 1, 2, 4, 6, and 8 weeks postfracture with outcome measures of histology, biomechanical strength testing, pQCT, relative BMD, and motion detection. OVX animals had significantly lower BMD, slower fracture repair (histologically), reduced stiffness in the fractured femora (8 weeks) and strength in the contralateral femora (6 and 8 weeks), increased body weight, and decreased motion. This study has demonstrated that OVX is associated with decrease in BMD (particularly in trabecular bone) and a reduction in the mechanical properties of intact bone and healing fractures. The histological, biomechanical, and radiological measures of union suggest that OVX delayed fracture healing. (C) 2007 Orthopaedic Research Society. Published by Wiley Periodicals.

The application of calcined natural dolomitic rock as a solid base catalyst in triglyceride transesterification for biodiesel synthesis

Natural dolomitic rock has been investigated in the transesterification of C-4 and C-8 triglycerides and olive oil with a view to determining its viability as a solid base catalyst for use in biodiesel synthesis. XRD reveals that the dolomitic rock comprised 77% dolomite and 23% magnesian calcite. The generation of basic sites requires calcination at 900 degrees C, which increases the surface area and transforms the mineral into MgO nanocrystallites dispersed over CaO particles. Calcined dolomitic rock exhibits high activity towards the liquid phase transesterification of glyceryl tributyrate and trioctanoate, and even olive oil, with methanol for biodiesel production.

Polymer-supported phosphoramidites: highly efficient and recyclable catalysts for asymmetric hydrogenation of dimethylitaconate and dehydroamino acids and esters

Several novel phosphoramidites have been prepared by reaction of the primary amines para-vinylaniline, ortho-anisidine, 2-methoxyphenyl(4-vinylbenzyl)amine, 8-aminoquinoline and 3-vinyl-8-aminoquinoline with (S)-1,1'-bi-2-naphthylchlorophosphite, in the presence of base. Rhodium(l) complexes of these phosphoramidites catalyse the asymmetric hydrogenation of dimethylitaconate and dehydroamino acids and esters giving ee values up to 95%. Soluble non-cross linked polymers of the para-vinylaniline and 3-vinyl-8-aminoquinoline-based phosphoramidites have been prepared by free radical co-polymerisation with styrene in the presence of AIBN as initiator. The corresponding [Rh(COD)](+) complexes serve as recyclable catalysts for the asymmetric hydrogenation dimethylitaconate and dehydroamino acids and esters to give ee values up to 80%. (C) 2003 Elsevier Science Ltd. All rights reserved.

Psychological problems in children with hemiplegia: a European multicentre survey

Objective: To describe the prevalence and determinants of psychological problems in European children with hemiplegia. Design: Cross-sectional survey. Setting: Home visits in nine European regions by research associates who administered standard questionnaires to parents. Patients: 279 children with hemiplegia aged 8–12 years were recruited from population-based case registers. Outcome measure: Strengths and Difficulties Questionnaire comprising emotion, conduct, hyperactivity, peer problems and prosocial domains. An “impact score” (IS) measures the social and psychological impact of the child’s difficulties. Results: Children with hemiplegia had higher mean scores on the total difficulties score (TDS) compared with a normative sample (p<0.001). 48% and 57% of children, respectively, had borderline–abnormal TDS and IS. Significant, independent associations were observed between intellectual impairment and an increased risk for hyperactivity (odds ratio; OR 8.4, 95% CI 3.4 to 20.8), peer problems (OR 3.1, 95% CI 1.7 to 5.5), psychological and social impact (OR 3.0, 95% CI 1.6 to 5.6) when children with an intellectual quotient (IQ) <50 were compared with those with an IQ >70. Boys had an increased risk for conduct (OR 2.1, 95% CI 1.2 to 3.7) and hyperactivity disorders (OR 2.5, 95% CI 1.4 to 4.6). Poor self-esteem was associated with an increased risk for peer problems (OR 5.8, 95% CI 2.5 to 13.4) and poor prosocial skills (OR 7.5, 95% CI 2.4 to 23.2) compared with those with high self-esteem. Other determinants of psychological adjustment were impaired communication, severe pain and living with a single parent. Conclusions: Many of the psychological problems identified are amenable to treatment. Special attention should be given to those at highest risk of developing psychological difficulties.

Survival of laboratory-reared juvenile European lobster (Homarus gammarus) from three brood sources in southwestern Norway

Experiments were carried out from June 2000 to April 2001 to compare survival of European lobster (Homarus gammarus) offspring (larvae and juveniles) from three brood sources, Kvitsøy Wild (KW), Kvitsøy Cultured (KC), and Rogaland Wild (RW), Norway. In the first set of experiments, newly hatched larvae (stage I) were raised in separate family tanks. All larvae groups survived to stage III/IV, although large variation in relative survival was observed among families within each of the three different female groups. Highest overall survival was observed for the RW group (12.8%), whereas no differences in overall survival were found between the KW (9.0%) and KC groups (9.6%). From stage III/IV, larvae from single family tank experiments were mixed in five “common garden” juvenile experiments. These lasted for 9 months, and the surviving juveniles were identified to family/female group using microsatellite DNA profiling. Significantly higher survival of the KW families (7.0%) was found compared with the KC (3.7%) and the RW families (3.2%), and differences in family ranking of relative survival values were evident between the KW and KC groups. The relative survival rate of the different groups was independent of female lobster size. An estimate based on only stage IV larvae reduced the difference in survival between the KW (11.4%) and KC (8.3%) group. The experiments provided evidence that cultured females (KC) are producing viable offspring with lower, but comparable survival to that of offspring from wild females (KW).