Mineralogy and interstitial-water chemistry of ODP Leg 101 sites

Concentrations of dissolved Ca2+, Sr2+, Mg2+, SO4[2-], and alkalinity were measured in pore waters squeezed from sediments taken from ODP Holes 626C and 626D in the Florida Straits; Holes 627A and 627B, 628A, and 630A and 630C north of Little Bahama Bank; Holes 631 A, 632A and 632B, and 633A in Exuma Sound; and Holes 634A and 635A and 635B in Northeast Providence Channel. These data are compared with the mineralogy and strontium content of the sediments from which the waters were squeezed. Contrasts in the geochemical profiles suggest that significantly different processes govern pore-water signatures at each group of sites. In Little Bahama Bank, strong positive Ca2+ gradients are correlated with weak negative Mg2+ profiles. These trends are analogous to those seen at DSDP sites where carbonate deposits immediately overlie mafic basement, but as the depth to basement may be in excess of 5000 m, we suggest that diffusion gradients are initiated by an underlying sedimentary unit. In contrast, Ca2+ and Mg2+ gradients in Exuma Sound are not developed to any appreciable extent over similar thicknesses of sediment. We suggest that the pore-water chemistry in these deposits is principally controlled by diagenetic reactions occurring within each sequence. The location and extent of carbonate diagenesis can be estimated from dissolved Sr2+ profiles. In Little Bahama Bank and Exuma Sound, Sr2+ concentrations reach a maximum value of between 700 and 1000 µmol/L. Although the depths at which these concentrations are achieved are different for the two areas, the corresponding age of the sediment at the dissolved Sr2+ maximum is similar. Consequently, the diffusive flux of Sr2+ and the calculated rates of recrystallization in the two areas are likewise of a similar magnitude. The rates of recrystallization we calculate are lower than those found in some DSDP pelagic sites. As the waters throughout most of the holes are saturated with respect to SrSO4, celestite precipitation may cause erroneously low Sr2+ production rates and, consequently, low calculated rates of recrystallization. We therefore encourage only the discriminate use of Sr2+ profiles in the quantification of diagenetic processes.

A cassette ligation strategy with thioether replacement of three Gly-Gly peptide bonds: Total chemical synthesis of the 101 residue protein early pregnancy factor [psi(CH2S)(28-29,56-57,76-77)]

The 101 residue protein early pregnancy factor (EPF), also known as human chaperonin 10, was synthesized from four functionalized, but unprotected, peptide segments by a sequential thioether ligation strategy. The approach exploits the differential reactivity of a peptide-NHCH2CH2SH thiolate with XCH2CO-peptides, where X = Cl or I/Br. Initial model studies with short functionalized (but unprotected) peptides showed a significantly faster reaction of a peptide-NHCH2CH2SH thiolate with a BrCH2CO-peptide than with a CICH2CO-peptide, where thiolate displacement of the halide leads to chemoselective formation of a thioether surrogate for the Gly-Gly peptide bond. This rate difference was used as the basis of a novel sequential ligation approach to the synthesis of large polypeptide chains. Thus, ligation of a model bifunctional N-alpha-chloroacetyl, C-terminal thiolated peptide with a second N-alpha-bromoacetyl peptide demonstrated chemoselective bromide displacement by the thiol group. Further investigations showed that the relatively unreactive N-alpha-chloroacetyl peptides could be activated by halide exchange using saturated KI solutions to yield the highly reactive No-iodoacetyl peptides. These findings were used to formulate a sequential thioether ligation strategy for the synthesis of EPF, a 101 amino acid protein containing three Gly-Gly sites approximately equidistantly spaced within the peptide chain. Four peptide segments or cassettes comprising the EPF protein sequence (BrAc-[EPF 78-101] 12, ClAc-[EPF 58-75]-[NHCH2CH2SH] 13, ClAc-[EPF 30-55]-[NHCH2CH2SH] 14, and Ac-[EPF 1-27]-[NHCH2CH2SH] 15) of EPF were synthesized in high yield and purity using Boc SPPS chemistry. In the stepwise sequential ligation strategy, reaction of peptides 12 and 13 was followed by conversion of the N-terminal chloroacetyl functional group to an iodoacetyl, thus activating the product peptide for further ligation with peptide 14. The process of ligation followed by iodoacetyl activation was repeated to yield an analogue of EPF (EPF psi(CH2S)(28-29,56-57,76-77)) 19 in 19% overall yield.

Guidance on the transfer of mentally disordered patients detained under the Mental Health (NI) Order 1986 to and from Hospitals in Great Britain - August 2011 (PDF 101 KB)

Guidance on the transfer of mentally disordered patients detained under the Mental Health (NI) Order 1986 to and from Hospitals in Great Britain - August 2011.

Tackling Equality and Targeting Social Need - Improving the Infrastucture (PDF 101 KB)

This paper considers two recent initiatives in Northern Ireland relating to targeting social need and inequalities. While the paper deals with each separately they should be seen as complementary. Therefore, many of the points made in relation to one are also pertinent to the other. åÊ