Guanidiniocarbonyl-pyrrole-aryl conjugates as nucleic acid sensors: switch of binding mode and spectroscopic responses by introducing additional binding sites into the linker

Two novel guanidiniocarbonyl pyrrole-pyrene conjugates 3 and 4 as spectroscopic probes for ds-polynucleotides were synthesized and their interaction with different ds-DNAs/RNAs studied. Compared to a previously reported first set of conjugates (1 and 2) the significant extension and increased rigidity of the central part of the structure resulted in a switch of DNA binding mode from intercalative (previously studied derivatives 1 and 2 with a nonbinding and flexible linker) to minor groove binding of the two novel guanidiniocarbonyl-pyrrole-pyrene conjugates 3 and 4. These two compounds interact strongly with ds-DNAs, but only weakly with ds-RNA. The newly incorporated heterocyclic moieties within the central part of the structure of 3 and 4 were able to control by steric and hydrogen-bonding effects the alignment of the molecules within various, structurally different forms of DNA minor grooves, whereby even small differences in the position of the attached pyrene within the groove were reflected in different fluorimetric responses. In addition, 3 and 4 revealed intriguing in vitro selectivity among various human tumour cell lines.     

On invariants of discrete series representations of classical p-adic groups

To an irreducible square integrable representation ?? of a classical p-adic group, M?glin has attached invariants Jord(??), ?? _cusp and ${\epsilon_\pi}$ . These triples classify square integrable representations modulo cuspidal data (assuming a natural hypothesis). The definition of these invariants in M?glin (J Eur Math Soc 4(2):143?C200, 2002) is rather simple??in terms of induced representations, except at one case when a coherent normalization of standard intertwining operators is required. In this paper we show how one can define this case also in terms of induced representations.     

Effective partitioning method for computing generalized inverses and their gradients

We extend the algorithm for computing {1}, {1, 3}, {1, 4} inverses and their gradients from [11] to the set of multiple-variable rational and polynomial matrices. An improvement of this extension, appropriate to sparse polynomial matrices with relatively small number of nonzero coefficient matrices as well as in the case when the nonzero coefficient matrices are sparse, is introduced. For that purpose, we exploit two effective structures form [6], which make use of only nonzero addends in polynomial matrices, and define their partial derivatives. Symbolic computational package MATHEMATICA is used in the implementation. Several randomly generated test matrices are tested and the CPU times required by two used effective structures are compared and discussed.     

Dynamical properties of a particle in a wave packet: Scaling invariance and boundary crisis

Some dynamical properties present in a problem concerning the acceleration of particles in a wave packet are studied. The dynamics of the model is described in terms of a two-dimensional area preserving map. We show that the phase space is mixed in the sense that there are regular and chaotic regions coexisting. We use a connection with the standard map in order to find the position of the first invariant spanning curve which borders the chaotic sea. We find that the position of the first invariant spanning curve increases as a power of the control parameter with the exponent 2/3. The standard deviation of the kinetic energy of an ensemble of initial conditions obeys a power law as a function of time, and saturates after some crossover. Scaling formalism is used in order to characterise the chaotic region close to the transition from integrability to nonintegrability and a relationship between the power law exponents is derived. The formalism can be applied in many different systems with mixed phase space. Then, dissipation is introduced into the model and therefore the property of area preservation is broken, and consequently attractors are observed. We show that after a small change of the dissipation, the chaotic attractor as well as its basin of attraction are destroyed, thus leading the system to experience a boundary crisis. The transient after the crisis follows a power law with exponent −2.     

Interatomic Coulombic decay in mixed NeKr clusters

We report the occurrence of interatomic Coulombic decay (ICD) in mixed NeKr clusters. A well-defined feature ranging from 9 to 12 eV in kinetic energy is observed in coincidence with the Ne 2s photoelectrons. It derives from an ICD process, in which an initial Ne 2s vacancy is filled by a Ne 2p electron and an electron is emitted from a 4p level on a neighboring Kr atom. We have studied the dependence of the effect on photon energy, cluster composition, and cluster size. Interestingly, the ICD electron energy increases slightly and grows a shoulder on going from 2% to 5% Kr in the coexpansion process, which we interpret in terms of surface versus bulk effects.     

Direct functionalization of (un)protected tetrahydroisoquinoline and isochroman under iron and copper catalysis: two metals, two mechanisms

A highly facile, straightforward synthesis of 1-(3-indolyl)-tetrahydroisoquinolines was developed using either simple copper or iron catalysts. N-protected and unprotected tetrahydroisoquinolines (THIQ) could be used as starting materials. Extension of the substrate scope of the pronucleophile from indoles to pyrroles and electron-rich arenes was realized. Additionally, methoxyphenylation is not limited to THIQ but can be carried out on isochroman as well, again employing iron and copper catalysis.     

Infrared-induced reactivity of N2O on small gas-phase rhodium clusters

Far- and mid-infrared multiple photon dissociation spectroscopy has been employed to study both the structure and surface reactivity of isolated cationic rhodium clusters with surface-adsorbed nitrous oxide, Rh(n)N(2)O(+) (n = 4-8). Comparison of experimental spectra recorded using the argon atom tagging method with those calculated using density functional theory (DFT) reveals that the nitrous oxide is molecularly bound on the rhodium cluster via the terminal N-atom. Binding is thought to occur exclusively on atop sites with the rhodium clusters adopting close-packed structures. In related, but conceptually different experiments, infrared pumping of the vibrational modes corresponding with the normal modes of the adsorbed N(2)O has been observed to result in the decomposition of the N(2)O moiety and the production of oxide clusters. This cluster surface chemistry is observed for all cluster sizes studied except for n = 5. Plausible N(2)O decomposition mechanisms are given based on DFT calculations using exchange-correlation functionals. Similar experiments pumping the Rh-O stretch in Rh(n)ON(2)O(+) complexes, on which the same chemistry is observed, confirm the thermal nature of this reaction.     

Free energy and entropy production in planar Couette flow far from equilibrium

The macroscopic thermodynamic stability of a system of 108 diatomic molecules undergoing planar Couette flow far from equilibrium is reported. The system is perturbed from the steady state using a nondissipative variable colour field which induces a polarization in the system. It is found that the steady state for the system corresponds to an extremum in the generalized free energy and entropy production. However, while the free energy is always a minimum, the entropy production may be either a minimum or a maximum depending upon the direction of the colour field. These results, for a molecular system, are fundamentally different from those for an equivalent atomic system.     

A study of a polysulfone membrane for use in an in-situ tunable microdialysis probe during monitoring of starch enzymatic hydrolysates

We report a study made on a 5 kDa molecular weight cut-off (MWCO) polysulfone membrane (SPS 4005) for use in microdialysis sampling of starch enzymatic hydrolysates on-line coupled to column liquid chromatography with integrated pulsed electrochemical detection. Membrane characteristics were evaluated by examining both the membrane and membrane support layer using a scanning electron microscope (SEM). This study was made so as to elucidate the mechanism or mode by which a membrane exposed to different bioprocess conditions is either fouled or destroyed. The correlation of extraction fraction data with SEM was a confirmatory test for the observed change in the membrane characteristics. Examinations were made after keeping the membrane in pure water for 5, 10 and 30 min at room temperature or after perfusing the membrane with pure water continuously at room temperature, 60 and 90°C for 24 h. Extraction fractions were evaluated at these temperatures to see applicability of the SPS 4005 membrane to high temperature bioprocesses. Scanning electron microscopy studies were also made on membranes used for sampling and sample clean-up during on-line monitoring of the hydrolysis of soluble starch (according to Zulkowsky) for 32 h, and the hydrolysis of wheat starch at room temperature, 60 and 90°C for 6 h. Non-specific/directed protein-membrane interactions were evaluated by sampling maltoheptaose with a microdialysis probe fitted with a 10 mm SPS 4005 membrane, before and after treatment with an enzyme solution of Termamyl (endo-1,4-- -glucan glucanohydrolase EC 3.2.1.78).