Spectroscopic and computational insights into second-sphere amino-acid tuning of substrate analogue/active-site interactions in iron(III) superoxide dismutase

In this study, the mechanism by which second-sphere residues modulate the structural and electronic properties of substrate-analogue complexes of the Fe-dependent superoxide dismutase (FeSOD) has been explored. Both spectroscopic and computational methods were used to investigate the azide (N3(-)) adducts of Fe(3+)SOD (N3-Fe(3+)SOD) and its Q69E mutant, as well as Fe(3+)-substituted MnSOD (N3-Fe(3+)(Mn)SOD) and its Y34F mutant. Electronic absorption, circular dichroism, and magnetic circular dichroism spectroscopic data reveal that the energy of the dominant N3(-)-->Fe(3+) ligand-to-metal charge transfer (LMCT) transition decreases in the order N3-Fe(3+)(Mn)SOD>N3-Fe(3+)SOD>Q69E N3-Fe(3+)SOD. Intriguingly, the LMCT transition energies correlate almost linearly with the Fe(3+/2+) reduction potentials of the corresponding Fe(3+)-bound SOD species in the absence of azide, which span a range of approximately 1 V (see the preceding paper). To explore the origin of this correlation, combined quantum mechanics/molecular mechanics (QM/MM) geometry optimizations were performed on complete enzyme models. The INDO/S-CI computed electronic transition energies satisfactorily reproduce the experimental trend in LMCT transition energies, indicating that the QM/MM optimized active-site models are reasonable. Density functional theory calculations on these experimentally validated active-site models reveal that the differences in spectral and electronic properties among the four N 3(-) adducts arise primarily from differences in the hydrogen-bond network involving the conserved second-sphere Gln (mutated to Glu in Q69E FeSOD) and the solvent ligand. The implications of our findings with respect to the mechanism by which the second-coordination sphere modulates substrate-analogue binding as well as the catalytic properties of FeSOD are discussed.     

Polymer encapsulated and stabilised blue-phase liquid crystal droplets

Polymer-encapsulated–polymer-stabilised blue-phase liquid crystals (LCs) are investigated. Encapsulated droplets are formed in a polyvinyl alcohol solution by emulsification, and blue-phase (BP) LCs in the droplets are stabilised via the polymerisation of reactive monomers to extend the BP temperature range. Polymer stabilised droplets are found to cause the expansion of the BP temperature range from 53°C to below 0°C. The effects of composition on droplet formation and the electro-optical behaviour and morphological properties of these droplets are reported.     

On Defining Sets of Full Designs with Block Size Three

A defining set of a t-(v, k, λ) design is a subcollection of its blocks which is contained in no other t-design with the given parameters, on the same point set. A minimal defining set is a defining set, none of whose proper subcollections is a defining set. The spectrum of minimal defining sets of a design D is the set {|M| | M is a minimal defining set of D}. We show that if a t-(v, k, λ) design D is contained in a design F, then for every minimal defining set d _D of D there exists a minimal defining set d _F of F such that \({d_D = d_F\cap D}\). The unique simple design with parameters \({{\left(v,k, {v-2\choose k-2}\right)}}\) is said to be the full design on v elements; it comprises all possible k-tuples on a v set. Every simple t-(v, k, λ) design is contained in a full design, so studying minimal defining sets of full designs gives valuable information about the minimal defining sets of all t-(v, k, λ) designs. This paper studies the minimal defining sets of full designs when t = 2 and k = 3. Several families of non-isomorphic minimal defining sets of these designs are found. For given v, a lower bound on the size of the smallest and an upper bound on the size of the largest minimal defining set are given. The existence of a continuous section of the spectrum comprising approximately v values is shown, where just two values were known previously.     

Ruthenium(II)-NHC-catalyzed (NHC = perhydrobenzimidazol-2-ylidene) alkylation of amines using the hydrogen borrowing methodology under solvent-free conditions

Transition Metal Chemistry - New ruthenium(II) complexes with N-heterocyclic carbene ligand were synthesized by transmetalation reactions between silver(I) N-heterocyclic carbene complexes and...     

Generalized Derivations with Engel Conditions on One-Sided Ideals

Let R be a noncommutative prime ring and I a nonzero left ideal of R. Let g be a generalized derivation of R such that [g(r ^k ), r ^k ] _n  = 0 for all r ∈ I, where k, n are fixed positive integers. Then there exists c ∈ U, the left Utumi quotient ring of R, such that g(x) = xc and I(c ? α) = 0 for a suitable α ∈ C. In particular we have that g(x) = α x, for all x ∈ I.     

On Minimal Defining Sets of Full Designs and Self-Complementary Designs, and a New Algorithm for Finding Defining Sets of t-Designs

A defining set of a t-(v, k, λ) design is a partial design which is contained in a unique t-design with the given parameters. A minimal defining set is a defining set, none of whose proper partial designs is a defining set. This paper proposes a new and more efficient algorithm that finds all non-isomorphic minimal defining sets of a given t-design. The complete list of minimal defining sets of 2-(6, 3, 6) designs, 2-(7, 3, 4) designs, the full 2-(7, 3, 5) design, a 2-(10, 4, 4) design, 2-(10, 5, 4) designs, 2-(13, 3, 1) designs, 2-(15, 3, 1) designs, the 2-(25, 5, 1) design, 3-(8, 4, 2) designs, the 3-(12, 6, 2) design, and 3-(16, 8, 3) designs are given to illustrate the efficiency of the algorithm. Also, corrections to the literature are made for the minimal defining sets of four 2-(7, 3, 3) designs, two 2-(6, 3, 4) designs and the 2-(21, 5, 1) design. Moreover, an infinite class of minimal defining sets for 2-((v) || 3){v\choose3} designs, where v ≥ 5, has been constructed which helped to show that the difference between the sizes of the largest and the smallest minimal defining sets of 2-((v) || 3){v\choose3} designs gets arbitrarily large as v → ∞. Some results in the literature for the smallest defining sets of t-designs have been generalized to all minimal defining sets of these designs. We have also shown that all minimal defining sets of t-(2n, n, λ) designs can be constructed from the minimal defining sets of their restrictions when t is odd and all t-(2n, n, λ) designs are self-complementary. This theorem can be applied to 3-(8, 4, 3) designs, 3-(8, 4, 4) designs and the full 3-(8 || 4)3-{8 \choose 4} design using the previous results on minimal defining sets of their restrictions. Furthermore we proved that when n is even all (n − 1)-(2n, n, λ) designs are self-complementary.     

Notes on Jordan (σ, τ)*-derivations and Jordan triple (σ, τ)*-derivations

Let R be a 2-torsion free semiprime *-ring, σ, τ two epimorphisms of R and f, d : R → R two additive mappings. In this paper we prove the following results: (i) d is a Jordan (σ, τ)*-derivation if and only if d is a Jordan triple (σ, τ)*-derivation. (ii) f is a generalized Jordan (σ, τ)*-derivation if and only if f is a generalized Jordan triple (σ, τ)*-derivation.