A Density Functional Theory Study on the Active Center of Fe-Only Hydrogenase: Characterization and Electronic Structure of the Redox States

We have carried out extensive density functional theory (DFT) calculations for possible redox states of the active center in Fe-only hydrogenases. The active center is modeled by [(H(CH(3))S)(CO)(CN(-))Fe(p)(mu-DTN)(mu-CO)Fe(d)(CO)(CN(-))(L)](z) (z is the net charge in the complex; Fe(p)= the proximal Fe, Fe(d) = the distal Fe, DTN = (-SCH(2)NHCH(2)S-), L is the ligand that bonds with the Fed at the trans position to the bridging CO). Structures of possible redox states are optimized, and CO stretching frequencies are calculated. By a detailed comparison of all the calculated structures and the vibrational frequencies with the available experimental data, we find that (i) the fully oxidized, inactive state is an Fe(II)-Fe(II) state with a hydroxyl (OH(-)) group bonded at the Fe(d), (ii) the oxidized, active state is an Fe(II)-Fe(l) complex which is consistent with the assignment of Cao and Hall (J. Am. Chem. Soc. 2001, 123, 3734), and (iii) the fully reduced state is a mixture with the major component being a protonated Fe(l)-Fe(l) complex and the other component being its self-arranged form, Fe(II)-Fe(II) hydride, Our calculations also show that the exogenous CO can strongly bond with the Fe(II)-Fe(l) species, but cannot bond with the Fe(l)-Fe(l) complex. This result is consistent with experiments that CO tends to inhibit the oxidized, active state, but not the fully reduced state. The electronic structures of all the redox states have been analyzed. It is found that a frontier orbital which is a mixing state between the e(g) of Fe and the 2pi of the bridging CO plays a key role concerning the reactivity of Fe-only hydrogenases: (1) it is unoccupied in the fully oxidized, inactive state, half-occupied in the oxidized, active state, and fully occupied in the fully reduced state; (ii) the e(g)-2pi orbital is a bonding state, and this is the key reason for stability of the low oxidation states, such as Fe(l)-Fe(l) complexes; and (iii) in the e(g)-2pi orbital more charge accumulates between the bridging CO and the Fe(d) than between the bridging CO and the Fe(p), and the occupation increase in this orbital will enhance the bonding between the bridging CO and the Fe(d), leading to the bridging-CO shift toward the Fe(d).

The Influence of Child Protection Orientation on Child Welfare Practice

This article reports the findings of the second part of a two-part research project examining the potential for social workers to make changes in their work with families and children. While social workers in the United Kingdom have been encouraged to shift from a child protection to a child welfare orientation in their practice, such changes have been hampered by professional and organisational concern to manage risk. The research explores the influence of a child protection orientation on practice in child welfare cases. The findings, from two file analyses and interviews with twenty-six social workers, indicate that such an influence is indeed apparent. This is evidenced in two ways; firstly patterns of practice in child welfare cases are similar to those in child protection cases. Secondly, while the majority of social workers express an attitudinal desire to move towards a child welfare orientation, they still prioritise the management of risk in their practice. It is argued that social workers need permission from their employing organisations to make changes in their practice. This, in turn, requires such organisations to state clear goals in line with a child welfare orientation and develop holistic strategies to achieve these.

Parents' Views on Social Work Interventions in Child Welfare Cases

This article reports the findings of the third part of a three-part research project examining the potential for social workers to shift from a child protection to a child welfare orientation in their practice. Whilst social workers in the United Kingdom have been encouraged to make such changes they have been hampered by concerns to manage risk. Findings from the first two parts of the project had indicated that there was potential for a substantial proportion of child protection work to be redesignated as child welfare work, but that were this was achieved in practice there was evidence of continued influence of child protection processes as social workers sought to manage the risks inherent in child welfare cases. The study reported here sets out to ascertain the views of parents who were subject to child welfare interventions. The findings indicate that while parents feel apprehension with regard to contact with social workers, in the majority of cases successful relationships are formed. It is argued that social workers display considerable skill in monitoring potential risks whilst engaging with families and that the subtleties involved in such activity are not captured by official measures of governance which concentrate on more abstract indicators of performance.

Care proceedings: Exploring the relationship between case duration and achieving permanency for the child

The 1989 Children Act in England and Wales and the derivative 1995 Children (NI) Order in Northern Ireland provide the legislative framework within which issues pertaining to the care and supervision of children that come before the Courts are examined. Both pieces of legislation were intended to address a number of problems with the way that such issues were dealt with by the Court, particularly the tendency for proceedings to become protracted and for children to ‘drift’ in care as a consequence. The imposition of the ‘No Delay’ principle in both jurisdictions was designed specifically to address these concerns. However, since the introduction of both the 1989 Children Act (implemented in October 1991) and the 1995 Children (NI) Order (implemented in November 1996), there has been a steady increase in the average duration of proceedings and concerns remain about the impact that this may be having upon the children involved. This paper presents the findings of a research study (McSherry et al., 2004) that explored the complex relationship between the duration of care proceedings and costs to children in terms of the likelihood of achieving permanency.