HOX GENES: Seductive Science, Mysterious Mechanisms

HOX genes are evolutionarily highly conserved. The HOX proteins which they encode are master regulators of embryonic development and continue to be expressed throughout postnatal life. The 39 human HOX genes are located in four clusters (A-D) on different chromosomes at 7p15, 17q21.2, 12q13, and 2q31 respectively and are assumed to have arisen by duplication and divergence from a primordial homeobox gene. Disorders of limb formation, such as hand-foot-genital syndrome, have been traced to mutations in HOXA13 and HOXD13. Evolutionary conservation provides unlimited scope for experimental investigation of the functional control of the Hox gene network which is providing important insights into human disease. Chromosomal translocations involving the MLL gene, the human homologue of the Drosophila gene trithorax, create fusion genes which exhibit gain of function and are associated with aggressive leukaemias in both adults and children. To date 39 partner genes for MLL have been cloned from patients with leukaemia. Models based on specific translocations of MLL and individual HOX genes are now the subject of intense research aimed at understanding the molecular programs involved, and ultimately the design of chemotherapeutic agents for leukaemia. Investigation of the role of HOX genes in cancer has led to the concept that oncology may recapitulate ontology, a challenging postulate for experimentalists in view of the functional redundancy implicit in the HOX gene network

Photophysical properties of [(norharmane)Re(CO)3 (L)]+ complexes (L = bpy, phen or dppz). Redox behavior of the excited states and their interaction with Calf Thymus DNA

The photochemical and photophysical properties of [(nHo)Re(CO)3(L)]+ complexes, where nHo = 9H-pyrido[3,4-b]indole and L = 2,2′ bipyridine (bpy), 1,10 phenantroline (phen) or dipyridil[3,2-a:2′3′-c]phenazine (dppz) were investigated by Laser Flash Photolysis (LFF) and Pulse Radiolysis (PR) techniques. While complexes with L = bpy or phen show absorption transients compatible with MLCTRe→L excited states, [(nHo)Re(CO)3(dppz)]+ showed an excited state assignable to a dppz-centered, 3ππ*dppz. In aqueous solutions, the last complex does not generate any absorption transient. However, when Calf thymus DNA was added, the same absorption spectrum was obtained. These results suggest that this complex can intercalate into DNA. The species generated in either reductive or oxidative conditions in LFF experiments were compared with those obtained in PR. Also, the quenching rate constants (kq) of the excited states with MV2+ were calculated. The intercalation of the [(nHo)Re(CO)3(dppz)]+ into DNA, increases kq ∼100 times. This result is rationalized in terms of the conditions created by the intercalation using the biopolymer as a well-organized matrix.Fil: Maisuls, Iván. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Cabrerizo, Franco Martín. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); ArgentinaFil: Lappin, Alexander G.. University of Notre Dame-Indiana; Estados UnidosFil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Ferraudi, Guillermo J.. University of Notre Dame-Indiana; Estados Unido

Photochemical properties of a Re(I) polymer containing dppz in its structure : An interplay between dark and bright states of dppz

A new polymer, P4VP-Re(dppz), based on the poly-4-vinylpyridine structure containing Re(CO)3(dppz)⁺ pendants was synthesized. Multiple morphologies of P4VP-Re(dppz), such as vesicles, spherical nanoaggregates, large vesicle compounds, rings and pyramidal structures were observed by AFM and TEM in cast films of P4VP-Re(dppz) in solvents of different polarity and solvent/acid mixtures. Several conformations of a model monomer of P4VP-Re(dppz) were studied by TD-DFT to ascertain the effect of protonation over the molecular structure as well as over the absorption spectroscopy of P4VP-Re(dppz). P4VP-Re(dppz) excited states and their redox reactivity towards the sacrificial reductant TEOA were studied by flash photolysis experiments either in DMF and in DMF/HClO4. Those experiments were compared to the ones derived from thermal reactions of P4VP-Re(dppz) with solvated electrons in pulse radiolysis experiments. All the photophysical and photochemical properties studied were rationalized in terms of an interplay between 3IL(ππ*), 3MLCT(phz) and the 3MLCT(phen) states.Facultad de Ciencias ExactasInstituto de Investigaciones Fisicoquímicas Teóricas y AplicadasFacultad de Ingenierí

Photochemical properties of a Re(I) polymer containing dppz in its structure. An interplay between dark and bright states of dppz

A new polymer, P4VP-Re(dppz), based on the poly-4-vinylpyridine structure containing Re(CO)3(dppz)+ pendants was synthesized. Multiple morphologies of P4VP-Re(dppz), such as vesicles, spherical nanoaggregates, large vesicle compounds, rings and pyramidal structures were observed by AFM and TEM in cast films of P4VP-Re(dppz) in solvents of different polarity and solvent/acid mixtures. Several conformations of a model monomer of P4VP-Re(dppz) were studied by TD-DFT to ascertain the effect of protonation over the molecular structure as well as over the absorption spectroscopy of P4VP-Re(dppz). P4VP-Re(dppz) excited states and their redox reactivity towards the sacrificial reductant TEOA were studied by flash photolysis experiments either in DMF and in DMF/HClO4. Those experiments were compared to the ones derived from thermal reactions of P4VP-Re(dppz) with solvated electrons in pulse radiolysis experiments. All the photophysical and photochemical properties studied were rationalized in terms of an interplay between 3IL(ππ*), 3MLCT(phz) and the 3MLCT(phen) states.Fil: Saavedra Moncada, Alejandra. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Gutiérrez Pineda, Eduart Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional de La Plata; ArgentinaFil: Maisuls, Iván. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Lappin, Alexander G.. University of Notre Dame; Estados UnidosFil: Ferraudi, Guillermo J.. University of Notre Dame; Estados UnidosFil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentin

Photophysics, photochemistry and thermally-induced redox reactions of a (Pterin)rhenium(I) complex

In this work, we present a whole and deep study on the thermal redox and the photophysical and photochemical reactions of a tricarbonyl Re(I) complex coordinating Pterin, fac-ReI(CO)3(pterin)(H2O) (pterin = 2-amino-4-oxo-3H-pteridine). In aqueous solutions, the fluorescence of the complex is attributed to the emitting 1IL state (τemi ∼ 7.6 ns). In MeCN, however, the luminescence was ascribed to an overlapping dual emission from 1IL and 3MLCT states (τemi1 = 8.0 ns and τemi2 = 1.0 μs). Oxygen quenching of the 3MLCT based luminescence occurred with kq = 1.6 × 109 M−1 s−1. In glasses at 77 K, nevertheless, the 3MLCT prevailed over 1IL states. Flash photolysis experiments in aqueous solutions showed the spectrum of 3IL while in MeCN the presence of 3MLCT was evident. Pulse radiolysis experiments under oxidizing and reducing environments were performed in aqueous solutions of the Re-Pterin complex. By performing multivariate curve resolution − alternating least-squares (MCR-ALS), two species were identified under reducing conditions: an intermediate related to the semireduced radical of pterin ligand and the dihydrogenated [Re(CO)3(7,8-PtrH2)(H2O)] product. TD-DFT calculations helped to ascertain the nature of these species. Flash photolysis experiments where the excited states were reduced with triethylamine were in good agreement with pulse radiolysis experiments under reductive conditions. The oxidized transient spectrum was also obtained by pulse radiolysis, which compares very well with those published for Re(II) species, leading us to propose oxidation in the metal core as the reaction product of the transient under oxidizing conditions. The combination of different spectroscopic techniques along with the theoretical calculation allowed elucidating the nature, dynamics and reactivity of the excited states prevail in a Re-Pterin complex. This is of the particular importance considering that equivalent studies have not been reported for any other rhenium complex of substituted pterins nor for complexes of other transition metal ions of pterin derivatives.Fil: Ragone, Fabricio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: David Gara, Pedro Maximiliano. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigaciones Ópticas. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigaciones Ópticas. Universidad Nacional de La Plata. Centro de Investigaciones Ópticas; ArgentinaFil: Garcia Einschlag, Fernando Sebastian. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Lappin, Alexander G.. University of Notre Dame; Estados UnidosFil: Ferraudi, Guillermo J.. University of Notre Dame; Estados UnidosFil: Wolcan, Ezequiel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; ArgentinaFil: Ruiz, Gustavo Teodosio. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas; Argentin

Photophysical properties of [(norharmane)Re(CO)3 (L)]+ complexes (L = bpy, phen or dppz): redox behavior of the excited states and their interaction with Calf Thymus DNA

The photochemical and photophysical properties of [(nHo)Re(CO)3(L)]+ complexes, where nHo = 9H-pyrido[3,4-b]indole and L = 2,2′ bipyridine (bpy), 1,10 phenantroline (phen) or dipyridil[3,2-a:2′3′-c]phenazine (dppz) were investigated by Laser Flash Photolysis (LFF) and Pulse Radiolysis (PR) techniques. While complexes with L = bpy or phen show absorption transients compatible with MLCTRe→L excited states, [(nHo)Re(CO)3(dppz)]+ showed an excited state assignable to a dppz-centered, 3ππ*dppz. In aqueous solutions, the last complex does not generate any absorption transient. However, when Calf thymus DNA was added, the same absorption spectrum was obtained. These results suggest that this complex can intercalate into DNA. The species generated in either reductive or oxidative conditions in LFF experiments were compared with those obtained in PR. Also, the quenching rate constants (kq) of the excited states with MV2+ were calculated. The intercalation of the [(nHo)Re(CO)3(dppz)]+ into DNA, increases kq ∼100 times. This result is rationalized in terms of the conditions created by the intercalation using the biopolymer as a well-organized matrix.Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicada

Efecto de las propiedades morfológicas sobre las propiedades fotofísicas del grupo colgante -Re(CO)3(PHEN) unido al esqueleto de la poli-4-vinilpiridina

Las propiedades fotoquímicas y fotofísicas del polímero Re-P4VP, donde los cromóforos de -Re(I)(CO)3(phen) están unidos a la cadena de la poli-4-vinilpiridina, fueron interpretadas en base a las transformaciones morfológicas del mismo. La morfología del Re-P4VP se estudió bajo diferentes medios y condiciones de concentración por las técnicas de TEM y AFM. Los resultados de estos estudios en Re-P4VP y Re-P4VP en presencia de HClO4, Re-P4VPHnn+, revelaron que sus morfologías son dependientes de la concentración del polímero de Re(I). Estos cambios morfológicos tienen una influencia directa en las propiedades fotofísicas del polímero de Re-P4VP, siendo responsables de un incremento significativo del tiempo de vida del estado excitado MLCTRe(I) ? phen con la concentración del polímero y de un aumento de casi 8 veces en el rendimiento cuántico de luminiscencia después de la protonación del Re-P4VP.Facultad de Ciencias Agrarias y Forestale

Male Weaponry in a Fighting Cricket

Sexually selected male weaponry is widespread in nature. Despite being model systems for the study of male aggression in Western science and for cricket fights in Chinese culture, field crickets (Orthoptera, Gryllidae, Gryllinae) are not known to possess sexually dimorphic weaponry. In a wild population of the fall field cricket, Gryllus pennsylvanicus, we report sexual dimorphism in head size as well as the size of mouthparts, both of which are used when aggressive contests between males escalate to physical combat. Male G. pennsylvanicus have larger heads, maxillae and mandibles than females when controlling for pronotum length. We conducted two experiments to test the hypothesis that relatively larger weaponry conveys an advantage to males in aggressive contests. Pairs of males were selected for differences in head size and consequently were different in the size of maxillae and mandibles. In the first experiment, males were closely matched for body size (pronotum length), and in the second, they were matched for body mass. Males with proportionately larger weaponry won more fights and increasing differences in weaponry size between males increased the fighting success of the male with the larger weaponry. This was particularly true when contests escalated to grappling, the most intense level of aggression. However, neither contest duration nor intensity was related to weaponry size as predicted by models of contest settlement. These results are the first evidence that the size of the head capsule and mouthparts are under positive selection via male-male competition in field crickets, and validate 800-year-old Chinese traditional knowledge

Insights into the Ecology and Evolutionary Success of Crocodilians Revealed through Bite-Force and Tooth-Pressure Experimentation

BackgroundCrocodilians have dominated predatory niches at the water-land interface for over 85 million years. Like their ancestors, living species show substantial variation in their jaw proportions, dental form and body size. These differences are often assumed to reflect anatomical specialization related to feeding and niche occupation, but quantified data are scant. How these factors relate to biomechanical performance during feeding and their relevance to crocodilian evolutionary success are not known.Methodology/Principal FindingsWe measured adult bite forces and tooth pressures in all 23 extant crocodilian species and analyzed the results in ecological and phylogenetic contexts. We demonstrate that these reptiles generate the highest bite forces and tooth pressures known for any living animals. Bite forces strongly correlate with body size, and size changes are a major mechanism of feeding evolution in this group. Jaw shape demonstrates surprisingly little correlation to bite force and pressures. Bite forces can now be predicted in fossil crocodilians using the regression equations generated in this research.Conclusions/SignificanceCritical to crocodilian long-term success was the evolution of a high bite-force generating musculo-skeletal architecture. Once achieved, the relative force capacities of this system went essentially unmodified throughout subsequent diversification. Rampant changes in body size and concurrent changes in bite force served as a mechanism to allow access to differing prey types and sizes. Further access to the diversity of near-shore prey was gained primarily through changes in tooth pressure via the evolution of dental form and distributions of the teeth within the jaws. Rostral proportions changed substantially throughout crocodilian evolution, but not in correspondence with bite forces. The biomechanical and ecological ramifications of such changes need further examination