Recognition of DNA base pair mismatches by a cyclometalated Rh(III) intercalator

Two cyclometalated complexes of Rh(III), rac-[Rh(ppy)2chrysi]+ and rac-[Rh(ppy)2 phi]+, have been synthesized and characterized with respect to their binding to DNA. The structure of rac-[Rh(ppy)2 phi]Cl.H2O.CH2Cl2 has been determined by X-ray diffraction (monoclinic, P2(1)/c, Z = 4, a = 18.447(3) A, b = 9.770(1) A, c = 17.661(3) A, beta = 94.821(11) degrees, V = 3172.0(8) A3) and reveals that the complex is a distorted octahedron with nearly planar ligands, similar in structure to the DNA mismatch recognition agent [Rh(bpy)2chrysi]3+. The 2-phenylpyridyl nitrogen atoms are shown to be in the axial positions, as a result of trans-directing effects. This tendency simplifies the synthesis and purification of such complexes by limiting the number of possible isomers generated. The abilities of [Rh(ppy)2chrysi]+ and [Rh(ppy)2 phi]+ to bind and, with photoactivation, to cleave DNA have been demonstrated in assays on duplex DNA in the absence and presence of a single CC mismatch. [Rh(ppy)2chrysi]+ was shown upon photoactivation to cleave DNA selectively at the base pair mismatch whereas [Rh(ppy)2 phi]+ cleaves B-DNA nonspecifically. The reactivity of [Rh(ppy)2chrysi]+ was also compared to that of the known mismatch recognition agent [Rh(bpy)2chrysi]3+. Competitive photocleavage studies revealed that a 14-fold excess of [Rh(ppy)2chrysi]+ was required to achieve the same level of binding as that of [Rh(bpy)2chrysi]3+. However, the ratio of damage induced by [Rh(bpy)2chrysi]3+ to that induced by [Rh(ppy)2chrysi]+ is considerably greater than this value, indicating that decreased photoefficiency for the cyclometalated complex must contribute to its significantly attenuated photoreactivity. These cyclometalated intercalators provide the starting points for the design of a new family of metal complexes targeted to DNA.     

Connections Between Single-Level and Bilevel Multiobjective Optimization

The relationship between bilevel optimization and multiobjective optimization has been studied by several authors, and there have been repeated attempts to establish a link between the two. We unify the results from the literature and generalize them for bilevel multiobjective optimization. We formulate sufficient conditions for an arbitrary binary relation to guarantee equality between the efficient set produced by the relation and the set of optimal solutions to a bilevel problem. In addition, we present specially structured bilevel multiobjective optimization problems motivated by real-life applications and an accompanying binary relation permitting their reduction to single-level multiobjective optimization problems.     

Copper and copper oxide nanoparticles in a cellulose support studied using anomalous small-angle X-ray scattering

Microcrystalline cellulose is a porous natural material which can be used both as a support for nanoparticles and as a reducer of metal ions. Cellulose supported nanoparticles can act as catalysts in many reactions. Cu, CuO, and Cu₂O particles were prepared in microcrystalline cellulose by adding a solution of copper salt to the insoluble cellulose matrix and by reducing the copper ions with several reducers. The porous nanocomposites were studied using anomalous small angle X-ray scattering (ASAXS), X-ray absorption spectroscopy, and X-ray diffraction. Reduction of Cu²⁺ with cellulose in ammonium hydrate medium yielded crystalline CuO nanoparticles and the crystallite size was about 6–20 nm irrespective of the copper concentration. The size distribution of the CuO particles was determined with ASAXS measurements and coincided with the crystallite sizes. Using sodium borohydrate or hydrazine sulfate as a reducer both metallic Cu and Cu₂O nanoparticles were obtained and the crystallite size and the oxidation state depended on the amount of reducer.     

Langmuir-Blodgett films of hydrophobins HFBI and HFBII

Hydrophobins are small fungal proteins, which have remarkable surface-chemical properties. They self-assemble at hydrophobic/hydrophilic interfaces and work as adhesive agents and coatings. Sixteen layer Langmuir-Blodgett films of hydrophobins HFBI and HFBII from the fungus Trichoderma reesei were prepared and studied using grazing-incidence X-ray diffraction and reflectivity techniques. Both kind of films contain hexagonally ordered crystallites on the substrate with unit cell parameters of a = b = 54 Å (HFBI) and a = b = 55 Å (HFBII). The structure is similar to the structure of monolayer Langmuir-Blodgett films.     

Generalization of Matsui’s Algorithm 1 to linear hull for key-alternating block ciphers

We consider linear approximations of an iterated block cipher in the presence of several strong linear approximation trails. While the effect of such trails in Matsui’s Algorithm 2, also called the linear hull effect, has been previously studied by a number of authors, their effect on Matsui’s Algorithm 1 has not been investigated until now. The goal of this paper is to fill this gap and examine how to generalize Matsui’s Algorithm 1 to work also on linear hulls. We restrict to key-alternating ciphers and develop a mathematical framework for this kind of attacks. The complexity of the attack increases with the number of linear trails that have significant contribution to the correlation. We show how to reduce the number of trails and thus the complexity using related keys. Further, we illustrate our theory by experimental results on a reduced round version of the block cipher PRESENT.     

On the exceptional set in Goldbach’s problem in short intervals

Let 1/5 < θ ≤ 1. We prove that there exists a positive constant δ such that the number of even integers in the interval [X, X + X ^θ] which are not a sum of two primes is 《 X ^θ−δ. The proof uses the circle method, a sieve method, exponential sum estimates and zero-density estimates for L-functions. Current address: Department of Mathematics, 20014 University of Turku, Finland. Author’s address: Department of Mathematics, University of London, Royal Holloway, Egham, Surrey TW20 0EX, UK     

Probing the negative Wigner function of a pulsed single photon point by point

We investigate quantum properties of pulsed light fields point by point in phase space. We probe the negative region of the Wigner function of a single photon generated by the means of waveguided parametric down conversion. This capability is achieved by employing loss-tolerant photon-number resolving detection, allowing us to directly observe the oscillations of the photon statistics in dependence of applied displacements in phase space. Our scheme is highly mode sensitive and can reveal the single-mode character of the signal state.     

Quantitative determination of the main aliphatic carboxylic acids in wood kraft black liquors by high-performance liquid chromatography-mass spectrometry

The versatile characterization of organic material and especially of the significant aliphatic hydroxy acids in black liquor is of great importance, for example, in monitoring the progress of the kraft pulping process. This paper describes a simple high-performance liquid chromatographic separation method with atmospheric-pressure chemical ionization mass spectrometry (HPLC-APCI-MS) which was developed for the rapid quantitative analysis of these acids, mainly formed as the alkaline degradation products of feedstock carbohydrates. The fraction of carbohydrate degradation products is mainly composed of hydroxy monocarboxylic and volatile acids (formic and acetic acids) along with lesser amounts of various dicarboxylic acids. This method was thoroughly tested and validated to determine the most abundant nonvolatile low-molecular-mass aliphatic mono- and dicarboxylic acids present in softwood (pine and spruce) and hardwood (birch and aspen) kraft black liquors. This straightforward technique provides, compared to the conventional gas chromatographic methods, some important advantages such as simple sample preparation and a faster analysis time, thus enabling almost real-time monitoring of these acids.