Clustering of nucleosides in the presence of alkali metals: Biologically relevant quartets of guanosine,deoxyguanosine and uridine observed by ESI-MS/MS

Electrospray ionization (ESI) mass spectra of nucleosides, recorded in the presence of alkali metals, display alkali metal ion-bound quartets and other clusters that may have implications for understanding non-covalent interactions in DNA and RNA. The tetramers of guanosine and deoxyguanosine and also their metaclusters (clusters of clusters), cationized by alkali metals, were observed as unusually abundant magic number clusters. The observation of these species in the gas phase parallels previous condensed-phase studies, which show that guanine derivatives can form quartets and metaclusters of quartets in solution in the presence of metal cations. This parallel behavior and also internal evidence suggest that bonding in the guanosine tetramers involves the bases rather than the sugar units. The nucleobases thymine and uracil are known to form magic number pentameric adducts with K+, Cs+ and NH4+ in the gas phase. In sharp contrast, we now show that the nucleosides uridine and deoxythymidine do not form the pentameric clusters characteristic of the corresponding bases. More subtle effects of the sugars are evident in the fact that adenosine and cytidine form numerous higher order clusters with alkali metals, whereas deoxyadenosine and deoxycytidine show no clustering. It is suggested that hydrogen bonding between the bases in the tetramers of dG and rG are the dominant interactions in the clusters, hence changing the ribose group to deoxyribose (and vice versa) generally has little effect. However, the additional hydroxyl group of RNA nucleosides enhances the non-selective formation of higher-order aggregates for adenosine and cytidine and results in the lack of highly stable magic number clusters. Some clusters are the result of aggregation in the course of ionization (ESI) whereas others appear to be intrinsic to the solution being examined.     

Range-Renewal Processes: SLLNs and Power Laws*

Given n samples(viewed as an n-tuple) of a γ-regular discrete distribution π,in this article the authors concern with the weighted and unweighted graphs induced by the n samples. They first prove a series of SLLN results(of Dvoretzky-Erd¨os’ type). Then they show that the vertex weights of the graphs under investigation obey asymptotically power law distributions with exponent 1 + γ. They also give a conjecture that the degrees of unweighted graphs would exhibit asymptotically power law distribu...     

The peak and descent statistics over ballot permutations

A ballot permutation is a permutation π such that in any prefix of π the descent number is not more than the ascent number. By using a reversal-concatenation map, we (i) give a formula for the joint distribution (pk, des) of the peak and descent statistics over ballot permutations, (ii) connect this distribution and the joint distribution (pk, des) over ordinary permutations in terms of generating functions, and (iii) confirm Spiro's conjecture which finds the equidistribution of the descent statistic for ballot permutations and an analogue of the descent statistic for odd order permutations.     

Yet another way of calculating moments of the Kesten's distribution and its consequences for Catalan numbers and Catalan triangles

We calculate moments of the so-called Kesten distribution by means of the expansion of the denominator of the density of this distribution and then integrate all summands with respect to the semicircle distribution. By comparing this expression with the formulae for the moments of Kesten's distribution obtained by other means, we find identities involving polynomials whose power coefficients are closely related to Catalan numbers, Catalan triangles, binomial coefficients. Finally, as applications of these identities we obtain various interesting relations between the aforementioned numbers, also concerning Lucas, Fibonacci and Fine numbers.     

Weakly compactly generated Banach spaces and the strong law of large numbers

IfB is a weakly compactly generated Banach space andf: (S,S, ) satisfies the strong law of large numbers, thenf=f ₁+f ₂, wheref ₁ is Bochner -integrable andf ₂ is Pettis -integrable with Pettis norm 0. The decomposition is unique.     

Complete solutions of a family of quartic Thue and index form equations

Continuing the recent work of the second author, we prove that the diophantine equation

for has exactly 12 solutions except when , when it has 16 solutions. If denotes one of the zeros of , then for we also find all with .

     

Aurifeuillian factorizations and the period of the Bell numbers modulo a prime

We show that the minimum period modulo of the Bell exponential integers is for all primes and several larger . Our proof of this result requires the prime factorization of these periods. For some primes the factoring is aided by an algebraic formula called an Aurifeuillian factorization. We explain how the coefficients of the factors in these formulas may be computed.

     

Curvature and finite domination

Upper bounds obtained by Gromov on the Betti numbers of certain closed Riemannian manifolds are shown to be upper bounds on the minimum number of cells in --spaces dominating such manifolds.

     

Multicomponent electrolyte systems: Dependence of ionic mobilities on aqueous organic solvent structure

Ionic mobility data for multicomponent electrolyte systems at low concentrations are scarce due to experimental difficulties and are actually restricted to aqueous solutions of alkali chlorides. Some new results are presented which have been obtained by using a radiotracer method valid even if one of the ionic species is present at very low concentrations (tracer ion). The following electrolyte systems (two electrolytes with a common ion in a solvent) have been investigated at a 0.5N total ionic strength: NaNO₃–AgNO₃, KNO₃–AgNO₃, LiNO₃–AgNO₃ either in pure water or in water-rich (acetonitrile or dimethylsulfoxide) mixed solvents. Since ionic conductivity data processing by an extended law generalized to mixtures, such as that proposed by Quint and Viallard, has proved to be delicate to handle, our experimental results have been compared with the qualitative predictions of the classical Onsager-Fuoss limiting law. The main conclusion of this work is to give clear experimental evidence of the inability of any continuum theory to predict the ionic mobilities when solvent structural effect have to be taken into account. Consequently, the ionic behavior, particularly that of the Ag⁺ ion, has been interpreted in terms of preferential solvation and solvent microscopic structure. The trace mobility measurements reflect the maximum structural effect on the ionic transport properties.     

Electrical conduction nature and phase transition in CaTi1−x FexO3−δ (x = 0.1–0.5)

Transport numbers for oxygen ions and protons are measured by an emf method in the system CaTi_1?x Fe_xO_3?δ (x = 0.1–0.5) in the oxidizing and reducing atmospheres in the temperature interval 973–1173 K. It is shown that the compounds under study are mixed ion-electron conductors at small iron concentrations and electron conductors, at large iron contents. The proton conductivity in the compounds is very poor and does not exceed 0.5% in air. On the basis of the temperature dependences of transport numbers for ions and linear expansion, it is established that the CaTi_0.9Fe_0.1O_3?δ system has a phase transition of a second order in a reducing environment at 1020–1050 K. The total and partial electron conductivities of CaTi_0.9Fe_0.1O_3?δ are studied as a function of the partial pressure of oxygen at 1173 K. The nature of electroconduction in CaTi_1?x Fe_xO_3?δ is discussed.