Photo-induced double-strand DNA and site-specific protein cleavage activity of L-histidine (mu-oxo)diiron(III) complexes of heterocyclic bases

Three oxo-bridged diiron(III) complexes of L-histidine and heterocyclic bases [Fe-2(mu-O)(L-his)(2)(B)(2)](ClO4)(2) (1-3), where B is 2,2'-bipyridine (bpy),1,10-phenanthroline (phen), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq), were prepared and characterized. The bpy complex 1 was structurally characterized by X-ray crystallography. The molecular structure showed a {Fe-2(mu-O)} core in which iron(III) in a FeN4O2 coordination is bound to tridentate monoanionic L-histidine and bidentate bpy ligands. The Fe center dot center dot center dot Fe distance is similar to 3.5 angstrom. The Fe-O-Fe unit is essentially linear, giving a bond angle of similar to 172 degrees. The complexes showed irreversible cyclic voltammetric cathodic response near -0.1 V vs. SCE in H2O-0.1 M KCl. The binuclear units displayed antiferromagnetic interaction between two high-spin (S = 5/2) iron(III) centers giving a -J value of -110 cm(-1). The complexes showed good DNA binding propensity giving a binding constant value of similar to 10(5) M-1. Isothermal titration calorimetric data indicated single binding mode to the DNA. The binding was found to be driven by negative free energy change and enthalpy. The dpq complex 3 showed oxidative double-strand DNA cleavage on exposure to UV-A and visible light. The phen complex 2 displayed single-strand photocleavage of DNA. The DNA double-strand breaks were rationalized from theoretical molecular docking calculations. Mechanistic investigations showed formation of hydroxyl radicals as the reactive species through photodecarboxylation of the L-histidine ligand. The complexes exhibited good binding propensity to bovine serum albumin (BSA) protein in Tris-HCl/NaCl buffer medium. The dpq complex 3 showed UV-A light-induced site-specific oxidative BSA cleavage forming fragments of similar to 45 kDa and similar to 20 kDa molecular weights via SOH pathway.

Electricity pricing in New Zealand and the Australian State of Queensland: Accounting for the impact of sector restructuring

The electricity industries of New Zealand (NZ) and the Australian state of Queensland have undergone substantial structural and regulatory reform with the common intent to improve economic efficiency. Deregulation and privatisation have been key elements of the reform but have been approached differently by each jurisdiction. This study traces the link between structural and regulatory regimes and asset valuation, profits and, ultimately, pricing. The study finds that key drivers in recent price increases are the government-owned generation and retail sector in NZ and the government-owned distribution sector in Queensland. It is concluded that, contrary to the rationale for the imposition of regulatory controls in a nonmarket environment, the regulatory regimes appear to have contributed to higher rather than lower pricing structures.

Cyclic Peptide Disulfides - Solution And Solid-State Conformation Of Boc-Cys-Pro-Aib-Cys-S-S-Bridge-Nhme,A Disulfide-Bridged Peptide Helix

The solution and solid-state conformations of the peptide disulfide Boc-Cys-Pro-Aib-Cys-NHMe have been determined by NMR spectroscopy and X-ray diffraction. The Cys(4) and methylamide NH groups are solvent shielded in CDCI3 and (CD,),SO, suggesting their involvement in intramolecular hydrogen bonding. On the basis of known stereochemical preferences of Pro and Aib residues, a consecutive @-turn structure is favored in solution. X-ray diffraction analysis reveals a highly folded 310 helical conformation for the peptide, with the S-S bridge lying approximately parallel to the helix axis, linking residues 1 and 4. The backbone conformational angles are Cys(1) 4 = -121.1', $ = 65.6"; Pro(2) 4 = -58.9', 4 = -34.0'; Aib(3) 4 = -61.8', $ = -17.9'; Cys(4) 4 = -70.5', $ = -18.6'. Two intramolecular hydrogen bonds are observed between Cys(1) CO--HN Cys(4) and Pro(2) CO--HNMe. The disulfide bond has a right-handed chirality, with a dihedral angle (xss) of 82'.

Evaluation Of Diffusion-Coefficient And Ionic Mobility In (Nh4)4fe(Cn)6.1.5 H2o

The diffusion coefficient, D, and the ionic mobility, μ, in the protonic conductor ammonium ferrocyanide hydrate have been determined by the isothermal transient ionic current method. D is also determined from the time dependence of the build up of potential across the samples and theretical expressions describing this build up in terms of double exponential dependence on time are obtained. The values obtained are D=3.875×10−11m2s−1 and μ=1.65×10−9 m2V−1s−1.

A Magnetic Susceptibility Study of Spin-state Transitions in Rare-earth TrioxocobaItates( III)

Rare-earth trioxocobaltates(lll), Ln[CoO,], with Ln = Pr, Nd, Tb, Dy. and Yb exhibit low-spin to high-spin transitions of cobalt characterised by a maximum in the Ax-l against temperature plots where Ax is the cobalt contribution to the magnetic susceptibility. The susceptibility behaviour is distinct from that of La[CoO,] which shows a plateau in the x-I-T curve accompanied by a structural transition. The temperature at which the AX- I-T curve shows a maximum increases with the decrease in the size of the rare-earth ion. The susceptibility behavior of solid solutions of La,,Nd,CoO, has been investigated to see how the behaviour characteristic of Nd[CoO,] changes to that of La[CoO,].

State Estimates of Employment Rates for Persons with Disabilities: Report Summary

Statistics on the states’ employment rates for persons with disabilities relative to their non-disabled peers may be of assistance to providers of employment services for persons with disabilities. Such information can help service providers, policy makers, and disability advocacy leaders to assess whether the employment rate of people with disabilities is improving over time, given policy, regulatory, and service intervention strategies. A recent report from the Cornell University Rehabilitation Research and Training Center (RRTC) for Economic Research on Employment Policy for Persons with Disabilities uses data from the March Current Population Survey to estimate employment rates for persons with and without a disability in the non-institutionalized working-age (aged 25 through 61) civilian population in the United States, and for each state and the District of Columbia for the years 1980 through 1998. The employment rate of persons with a disability relative to that of persons without disabilities are found to vary greatly across states. Over the last 20 years the relative employment rate of those with a disability dramatically declined overall and in most states.

Steady-State Response of Thick Rectangular Plates

The classical theory of plates neglects the effects of rotatory inertia and shear deformation, and due to this assumption it is applicable only for thin plates. Mindlin presented an improved plate theory which is fairly accurate.

Reversible photodimerization of phenylbutadienes in the solid state

Based on x-ray crystallographic studies, it is shown that crystal chemical factors govern the reversible photodimerization of phenylbutadienes in the solid state.

Sequence-dependent conformation of an A-DNA double helix: The crystal structure of the octamer d(G-G-T-A-T-A-C-C)

The crystal structures of the synthetic self-complementary octamer d(G-G-T-A-T-A-C-C) and its 5-bromouracil-containing analogue have been refined to R values of 20% and 14% at resolutions of 1·8 and 2·25 Å, respectively. The molecules adopt an A-DNA type double-helical conformation, which is minimally affected by crystal forces. A detailed analysis of the structure shows a considerable influence of the nucleotide sequence on the base-pair stacking patterns. In particular, the electrostatic stacking interactions between adjacent guanine and thymine bases produce symmetric bending of the double helix and a major-groove widening. The sugar-phosphate backbone appears to be only slightly affected by the base sequence. The local variations in the base-pair orientation are brought about by correlated adjustments in the backbone torsion angles and the glycosidic orientation. Sequence-dependent conformational variations of the type observed here may contribute to the specificity of certain protein-DNA interactions.

Roles, responsibilities and scope of practice: describing the ‘state of play’ for infection control professionals in Australia and New Zealand

Background In the past decade the policy and practice context for infection control in Australia and New Zealand has changed, with infection control professionals (ICPs) now involved in the implementation of a large number of national strategies. Little is known about the current ICP workforce and what they do in their day-to-day positions. The aim of this study was to describe the ICP workforce in Australia and New Zealand with a focus on roles, responsibilities, and scope of practice. Methods A cross-sectional design using snowball recruitment was employed. ICPs completed an anonymous web-based survey with questions on demographics; qualifications held; level of experience; workplace characteristics; and roles and responsibilities. Chi-squared tests were used to determine if any factors were associated with how often activities were undertaken. Results A total of 300 ICPs from all Australian states and territories and New Zealand participated. Most ICPs were female (94%); 53% were aged over 50, and 93% were employed in registered nursing roles. Scope of practice was diverse: all ICPs indicated they undertook a large number and variety of activities as part of their roles. Some activities were undertaken on a less frequent basis by sole practitioners and ICPs in small teams. Conclusion This survey provides useful information on the current education, experience levels and scope of practice of ICPs in Australia and New Zealand. Work is now required to establish the best mechanisms to support and potentially streamline scope of practice, so that infection-control practice is optimised.

Two- and three-dimensional lead-1H-imidazole-4,5-dicarboxylates

Reaction of lead nitrate and 1H-imidazole-4,5-dicarboxylic acid under hydrothermal conditions carried out at different temperatures and pH yields a hybrid Compound Pb-2(1H-imidazole-4,5-dicarboxylate)2, 1, and a three-dimensional coordination polymer Pb(1H-imidazole-4,5-dicarboxylate), It. The two-dimensional double-layered compound, 1, with two-dimensional inorganic connectivities and one-dimensional organic connectivity is novel since hybrid compounds formed by 1H-imidazole-4,5-dicarboxylic acid are uncommon. The lead atoms in I have holodirectional geometry, while those in II show hemidirectionality. In both I and II, 1H-imidazole-4,5-dicarboxylic acid acts as a multi-dentate ligand with both the carboxylic groups and the amine group taking part in coordination. (C) 2009 Elsevier B.V. All rights reserved.

Double-authentication-preventing signatures

Digital signatures are often used by trusted authorities to make unique bindings between a subject and a digital object; for example, certificate authorities certify a public key belongs to a domain name, and time-stamping authorities certify that a certain piece of information existed at a certain time. Traditional digital signature schemes however impose no uniqueness conditions, so a trusted authority could make multiple certifications for the same subject but different objects, be it intentionally, by accident, or following a (legal or illegal) coercion. We propose the notion of a double-authentication-preventing signature, in which a value to be signed is split into two parts: a subject and a message. If a signer ever signs two different messages for the same subject, enough information is revealed to allow anyone to compute valid signatures on behalf of the signer. This double-signature forgeability property discourages signers from misbehaving—a form of self-enforcement—and would give binding authorities like CAs some cryptographic arguments to resist legal coercion. We give a generic construction using a new type of trapdoor functions with extractability properties, which we show can be instantiated using the group of sign-agnostic quadratic residues modulo a Blum integer; we show an additional application of these new extractable trapdoor functions to standard digital signatures.

On prequantization to reduce errors in double phase holograms

Prequantization has been forwarded as a means to improve the performance of double phase holograms (DPHs). We show here that any improvement (even under the best of conditions) is not large enough to help the DPH to compete favourably with other holograms.

Theory of the mixed valent state

After briefly discussing the question of a distinct mixed valent state and theoretical models for it, the area of greatest theoretical success, namely the mixed valent impurity, is reviewed. Applications to spectroscopy, energetics and Hall effect are then putlined. The independent impurity approximation is inadequate for many properties of the bulk system, which depend on lattice coherence. A recent auxiliary or slave boson approach with a simple mean field limit and fluctuation corrections is summarized. Finally the mixed valent semiconductor is discussed as an outstanding problem.