Experimental Evidence of the Occurrence of Intramolecular Electron Transfer in Catalyzed 1,2-Dioxetane Decomposition

The activation parameters for the thermal decomposition of 13 acridinium-substituted 1,2-dioxetanes, bearing an aromatic moiety, were determined and their chemiluminescence emission quantum yields estimated, utilizing in situ photosensitized 1,2-dioxetane generation and observation of its thermal decomposition kinetics, without isolation of these highly unstable cyclic peroxides. Decomposition rate constants show linear free-energy correlation for electron-withdrawing substituents, with a Hammett reaction constant of rho = 1.3 +/- 0.1, indicating the occurrence of an intramolecular electron transfer from the acridinium moiety to the 1,2-dioxetane ring, as postulated by the intramolecular chemically initiated electron exchange luminescence (CIEEL) mechanism. Emission quantum yield behavior can also be rationalized on the basis of the intramolecular CIEEL mechanism, additionally evidencing its occurrence in this transformation. Both relations constitute the first experimental evidence for the occurrence of the postulated intramolecular electron transfer in the catalyzed and induced decomposition of properly substituted 1,2-dioxetanes.

Antiparasitic, antineuroinflammatory, and cytotoxic polyketides from the marine sponge Plakortis angulospiculatus collected in Brazil

Investigation of the bioactive crude extract from the sponge Plakortis angulospiculatus from Brazil led to the isolation of plakortenone (1) as a new polyketide, along with five known polyketides (2-6) previously isolated from other Plakortis sponges. The known polyketides were tested in antileishmanial, antitrypanosomal, antineuroinflammatory, and cytotoxicity assays. The results show that plakortide P (3) is a potent antiparasitic compound, against both Leishmania chagasi and Trypanosona cruzi, and exhibited antineuroinflammatory activity. The known polyketides 2-6 were tested for cytotoxicity against four human cancer cell lines, but displayed only moderate cytotoxic activity.

NEONATAL HANDLING AND THE MATERNAL ODOR PREFERENCE IN RAT PUPS: INVOLVEMENT OF MONOAMINES AND CYCLIC AMP RESPONSE ELEMENT-BINDING PROTEIN PATHWAY IN THE OLFACTORY BULB

Early-life environmental events, such as the handling procedure, can induce long-lasting alterations upon several behavioral and neuroendocrine systems. However, the changes within the pups that could be causally related to the effects in adulthood are still poorly understood. In the present study, we analyzed the effects of neonatal handling on behavioral (maternal odor preference) and biochemical (cyclic AMP response element-binding protein (CREB) phosphorylation, noradrenaline (NA), and serotonin (5-HT) levels in the olfactory bulb (OB)) parameters in 7-day-old male and female rat pups. Repeated handling (RH) abolished preference for the maternal odor in female pups compared with nonhandled (NH) and the single-handled (SH) ones, while in RH males the preference was not different than NH and SH groups. In both male and female pups, RH decreased NA activity in the OB, but 5-HT activity increased only in males. Since preference for the maternal odor involves the synergic action of NA and 5-HT in the OB, the maintenance of the behavior in RH males could be related to the increased 5-HT activity, in spite of reduction in the NA activity in the OB. RH did not alter CREB phosphorylation in the OB of both male and females compared with NH pups. The repeated handling procedure can affect the behavior of rat pups in response to the maternal odor and biochemical parameters related to the olfactory learning mechanism. Sex differences were already detected in 7-day-old pups. Although the responsiveness of the hypothalamic-pituitary-adrenal axis to stressors is reduced in the neonatal period, environmental interventions may impact behavioral and biochemical mechanisms relevant to the animal at that early age. (C) 2009 IBRO. Published by Elsevier Ltd. All rights reserved.

Cyclic Maximal Ideals of Rings of Differential Operators over Power Series Rings

In [3], Bratti and Takagi conjectured that a first order differential operator S=11 +...+ nn+ with 1,..., n, {x1,..., xn} does not generate a cyclic maximal left (or right) ideal of the ring of differential operators. This is contrary to the case of the Weyl algebra, i.e., the ring of differential operators over the polynomial ring [x1,..., xn]. In this case, we know that such cyclic maximal ideals do exist. In this article, we prove several special cases of the conjecture of Bratti and Takagi.

CoMFA and CoMSIA 3D QSAR Models for a Series of Cyclic Imides with Analgesic Activity

Three-dimensional quantitative structure-activity relationships (3D-QSAR) were performed for a series of analgesic cyclic imides using the CoMFA and CoMSIA methods. Significant correlation coefficients ( CoMFA, r(2) = 0.95 and q(2) = 0.72; CoMSIA, r(2) = 0.96 and q(2) = 0.76) were obtained, and the generated models were externally validated using test sets. The final QSAR models as well as the information gathered from 3D contour maps should be useful for the design of novel cyclic imides having improved analgesic activity.

Classical and fragment-based hologram structure-activity relationships for a series of analgesic cyclic imides

Cyclic imides have been widely employed in drug design research due to their multiple pharmacological and biological properties. In the present study, two-dimensional quantitative structure-activity relationship (2D QSAR) studies were conducted on a series of potent analgesic cyclic imides using both classical and hologram QSAR (HQSAR) methods, yielding significant statistical models (classical QSAR, q(2) = 0.80; HQSAR, q(2) = 0.84). The models were then used to evaluate an external data test, and the predicted values were in good agreement with the experimental results, indicating their consistency for untested compounds.

On cohomologies and extensions of cyclic groups

Cohomology groups H(s)(Z(n), Z(m)) are studied to describe all groups up to isomorphism which are (central) extensions of the cyclic group Z(n) by the Z(n)-module Z(m). Further, for each such a group the number of non-equivalent extensions is determined. (C) 2011 Elsevier B.V. All rights reserved.

Polynomial identities for the ternary cyclic sum

We simplify the results of Bremner and Hentzel [J. Algebra 231 (2000) 387-405] on polynomial identities of degree 9 in two variables satisfied by the ternary cyclic sum [a, b, c] abc + bca + cab in every totally associative ternary algebra. We also obtain new identities of degree 9 in three variables which do not follow from the identities in two variables. Our results depend on (i) the LLL algorithm for lattice basis reduction, and (ii) linearization operators in the group algebra of the symmetric group which permit efficient computation of the representation matrices for a non-linear identity. Our computational methods can be applied to polynomial identities for other algebraic structures.

Bicyclic units, Bass cyclic units and free groups

Let G be a finite group and ZG its integral group ring. We show that if alpha is a nontrivial bicyclic unit of ZG, then there are bicyclic units beta and gamma of different types, such that and are non-abelian free groups. In the case when G is non-abelian of order coprime to 6 we prove the existence of a bicyclic unit u and a Bass cyclic unit v in ZG, such that < u(m), v > is a free non-abelian group for all sufficiently large positive integers m.

INVOLUTIONS AND FREE PAIRS OF BASS CYCLIC UNITS IN INTEGRAL GROUP RINGS

Let ZG be the integral group ring of the finite nonabelian group G over the ring of integers Z, and let * be an involution of ZG that extends one of G. If x and y are elements of G, we investigate when pairs of the form (u(k,m)(x*), u(k,m)(x*)) or (u(k,m)(x), u(k,m)(y)), formed respectively by Bass cyclic and *-symmetric Bass cyclic units, generate a free noncyclic subgroup of the unit group of ZG.

BASS CYCLIC UNITS AS FACTORS IN A FREE GROUP IN INTEGRAL GROUP RING UNITS

Marciniak and Sehgal showed that if u is a non-trivial bicyclic unit of an integral group ring then there is a bicyclic unit v such that u and v generate a non-abelian free group. A similar result does not hold for Bass cyclic units of infinite order based on non-central elements as some of them have finite order modulo the center. We prove a theorem that suggests that this is the only limitation to obtain a non-abelian free group from a given Bass cyclic unit. More precisely, we prove that if u is a Bass cyclic unit of an integral group ring ZG of a solvable and finite group G, such that u has infinite order modulo the center of U(ZG) and it is based on an element of prime order, then there is a non-abelian free group generated by a power of u and a power of a unit in ZG which is either a Bass cyclic unit or a bicyclic unit.

On Groups Whose Maximal Cyclic Subgroups Are Maximal

We consider the problem of classifying those groups whose maximal cyclic subgroups are maximal. We give a complete classification of those groups with this property and which are either soluble or residually finite.

Classification of the virtually cyclic subgroups of the pure braid groups of the projective plane

We classify the ( finite and infinite) virtually cyclic subgroups of the pure braid groups P(n)(RP(2)) of the projective plane. The maximal finite subgroups of P(n)(RP(2)) are isomorphic to the quaternion group of order 8 if n = 3, and to Z(4) if n >= 4. Further, for all n >= 3, the following groups are, up to isomorphism, the infinite virtually cyclic subgroups of P(n)(RP(2)): Z, Z(2) x Z and the amalgamated product Z(4)*(Z2)Z(4).

Stereoselective Nucleophilic Addition of Potassium Alkyltrifluoroborates to Cyclic N-Acyliminium Ions: a Simple and Mild Approach to Chiral 5-Alkyl-pyrrolidin-2-ones

The stereoselective nucleophilic addition of potassium alkyltrifluoroborates to cyclic N-acyliminium ions derived from N-benzyl-3,4,5-triacetoxy-pyrrolidin-2-one, which affords 5-substituted-pyrrolidin-2-ones, is described. The products are obtained in moderate to good yields and are produced predominantly as the anti diastereomer.

Deposition of selenium thin layers on gold surfaces from sulphuric acid media: Studies using electrochemical quartz crystal microbalance, cyclic voltammetry and AFM

In this paper we report here new considerations about the relationship between the mass and charge variations (m/z relationship) in underpotential deposition (UPD), bulk deposition and also in the H(2)Se formation reaction. Nanogravimetric experiments were able to show the adsorption of H(2)SeO(3) on the AuO surface prior to the voltammetric sweep and that, after the AuO reduction, 0.40 monolayer of H(2)SeO(3) remains adsorbed on the newly reduced Au surface, which was enough to gives rise to the UPD layer. The UPD results indicate that the maximum coverage with Se(ads) on polycrystalline gold surface corresponds to approximately 0.40 monolayer, in good agreement with charge density results. The cyclic voltammetry experiments demonstrated that the amount of bulk Se obtained during the potential scan to approximately 2 Se monolayers, which was further confirmed by electrochemical quartz crystal microbalance (EQCM) measurements that pointed out a mass variation corresponding of 3 monolayers of Se. In addition, the Se thin films were obtained by chronoamperometric experiments, where the Au electrode was polarized at +0.10V during different times in 1.0 M H(2)SO(4) + 1.0 mM SeO(2). The topologic aspects of the electrodeposits were observed in Atomic Force Microscope (AFM) measurements. Finally, in highly negative potential polarizations, the H(2)Se formation was analyzed by voltammetric and nanogravimetric measurements. These finding brings a new light on the selenium electrodeposition and point up to a proposed electrochemical model for molecule controlled surface engineering. (c) 2009 Elsevier Ltd. All rights reserved.