A Theoretical Investigation of the One– and Two–photon Properties of Porphyrins

The one‐ and two‐photon properties of free base porphin, free base porphin dianion, and the 2,4‐substituted diformyl and divinyl analogs of these molecules are studied using a semiempirical SCF‐MO formalism (CNDO‐π‐SCF‐MO‐PSDCI) including extensive single and double configuration interaction. Strongly two‐photon allowed states are predicted to lie in the Soret region as well as in the region between the Soret and visible bands. A number of the two‐photon allowed states in the Soret region are predicted to have two‐photon absorptivities exceeding 100×10−50 cm4 s molecule−1 photon−1. The calculations indicate that the visible (Q) states are well characterized by the four orbital model, whereas the Soret (B) states contain significant contributions from configurations comprised of other orbitals. The inclusion of extensive double configuration interaction significantly reduces the Soret‐visible (B–Q) splitting, increases the Qx–Qy splitting, and yields calculated oscillator strengths for the Qbands in better agreement with experiment than values calculated using single CI alone. The effects of conjugation into the porphyrin macrocycle are predicted to be more significant than inductive effects on macrocycle π orbitals due to substituent polarity. The 〈Qx‖r‖S0〉 and 〈Qy‖r‖S0〉 transition moment vectors are predicted to lie approximately through adjacent pyrrole rings in 2‐ and 4‐monoformyl free base porphin dianions and approximately through adjacent methine bridges in 2,4‐diformyl free base porphin dianion

Investigations of biomimetic light energy harvesting pigments

This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at Los Alamos National Laboratory (LANL). Nature uses chlorophyll and other porphyrinic pigments to capture and transfer light energy as a preliminary step in photosynthesis. The design of synthetic assemblies of light harvesting and energy directing pigments has been explored through synthesis and characterization of porphyrin oligomers. In this project, pigment electronic and vibrational structures have been explored by electrochemistry and dynamic and static optical measurements. Transient absorption data reveal energy transfer between pigments with lifetimes on the order of 20--200 picoseconds, while Raman data reveal that the basic porphyrin core structure is unperturbed relative to the individual monomer units. These two findings, along with an extensive series of experiments on the oxidized oligomers, reveal that coupling between the pigments is fundamentally weak, but sufficient to allow facile energy transfer as the predominant excited state process. Modeling of the expected quantum yields for energy transfer within a variety of arrays was accomplished, thereby providing a tool to guide synthetic goals

The geometry of Brauer graph algebras and cluster mutations.

In this paper we establish a connection between ribbon graphs and Brauer graphs. As a result, we show that a compact oriented surface with marked points gives rise to a unique Brauer graph algebra up to derived equivalence. In the case of a disc with marked points we show that a dual construction in terms of dual graphs exists. The rotation of a diagonal in an m-angulation gives rise to a Whitehead move in the dual graph, and we explicitly construct a tilting complex on the related Brauer graph algebras reflecting this geometrical move

A case of autism with an interstitial deletion on 4q leading to hemizygosity for genes encoding for glutamine and glycine neurotransmitter receptor sub-units (AMPA 2, GLRA3, GLRB) and neuropeptide receptors NPY1R, NPY5R

BACKGROUND: Autism is a pervasive developmental disorder characterized by a triad of deficits: qualitative impairments in social interactions, communication deficits, and repetitive and stereotyped patterns of behavior. Although autism is etiologically heterogeneous, family and twin studies have established a definite genetic basis. The inheritance of idiopathic autism is presumed to be complex, with many genes involved; environmental factors are also possibly contributory. The analysis of chromosome abnormalities associated with autism contributes greatly to the identification of autism candidate genes. CASE PRESENTATION: We describe a child with autistic disorder and an interstitial deletion on chromosome 4q. This child first presented at 12 months of age with developmental delay and minor dysmorphic features. At 4 years of age a diagnosis of Pervasive Developmental Disorder was made. At 11 years of age he met diagnostic criteria for autism. Cytogenetic studies revealed a chromosome 4q deletion. The karyotype was 46, XY del 4 (q31.3-q33). Here we report the clinical phenotype of the child and the molecular characterization of the deletion using molecular cytogenetic techniques and analysis of polymorphic markers. These studies revealed a 19 megabase deletion spanning 4q32 to 4q34. Analysis of existing polymorphic markers and new markers developed in this study revealed that the deletion arose on a paternally derived chromosome. To date 33 genes of known or inferred function are deleted as a consequence of the deletion. Among these are the AMPA 2 gene that encodes the glutamate receptor GluR2 sub-unit, GLRA3 and GLRB genes that encode glycine receptor subunits and neuropeptide Y receptor genes NPY1R and NPY5R. CONCLUSIONS: The deletion in this autistic subject serves to highlight specific autism candidate genes. He is hemizygous for AMPA 2, GLRA3, GLRB, NPY1R and NPY5R. GluR2 is the major determinant of AMPA receptor structure. Glutamate receptors maintain structural and functional plasticity of synapses. Neuropeptide Y and its receptors NPY1R and NPY5R play a role in hippocampal learning and memory. Glycine receptors are expressed in very early cortical development. Molecular cytogenetic studies and DNA sequence analysis in other patients with autism will be necessary to confirm that these genes are involved in autism

Investigating variation in replicability

Although replication is a central tenet of science, direct replications are rare in psychology. This research tested variation in the replicability of 13 classic and contemporary effects across 36 independent samples totaling 6,344 participants. In the aggregate, 10 effects replicated consistently. One effect – imagined contact reducing prejudice – showed weak support for replicability. And two effects – flag priming influencing conservatism and currency priming influencing system justification – did not replicate. We compared whether the conditions such as lab versus online or US versus international sample predicted effect magnitudes. By and large they did not. The results of this small sample of effects suggest that replicability is more dependent on the effect itself than on the sample and setting used to investigate the effect

Many Labs 2: Investigating Variation in Replicability Across Samples and Settings

We conducted preregistered replications of 28 classic and contemporary published findings, with protocols that were peer reviewed in advance, to examine variation in effect magnitudes across samples and settings. Each protocol was administered to approximately half of 125 samples that comprised 15,305 participants from 36 countries and territories. Using the conventional criterion of statistical significance (p < .05), we found that 15 (54%) of the replications provided evidence of a statistically significant effect in the same direction as the original finding. With a strict significance criterion (p < .0001), 14 (50%) of the replications still provided such evidence, a reflection of the extremely highpowered design. Seven (25%) of the replications yielded effect sizes larger than the original ones, and 21 (75%) yielded effect sizes smaller than the original ones. The median comparable Cohen’s ds were 0.60 for the original findings and 0.15 for the replications. The effect sizes were small (< 0.20) in 16 of the replications (57%), and 9 effects (32%) were in the direction opposite the direction of the original effect. Across settings, the Q statistic indicated significant heterogeneity in 11 (39%) of the replication effects, and most of those were among the findings with the largest overall effect sizes; only 1 effect that was near zero in the aggregate showed significant heterogeneity according to this measure. Only 1 effect had a tau value greater than .20, an indication of moderate heterogeneity. Eight others had tau values near or slightly above .10, an indication of slight heterogeneity. Moderation tests indicated that very little heterogeneity was attributable to the order in which the tasks were performed or whether the tasks were administered in lab versus online. Exploratory comparisons revealed little heterogeneity between Western, educated, industrialized, rich, and democratic (WEIRD) cultures and less WEIRD cultures (i.e., cultures with relatively high and low WEIRDness scores, respectively). Cumulatively, variability in the observed effect sizes was attributable more to the effect being studied than to the sample or setting in which it was studied.UCR::Vicerrectoría de Investigación::Unidades de Investigación::Ciencias Sociales::Instituto de Investigaciones Psicológicas (IIP

MELPHALAN AS AN IMMUNOMODULATOR IN THE ERADICATION OF ESTABLISHED TUMORS.

MELPHALAN AS AN IMMUNOMODULATOR IN THE ERADICATION OF ESTABLISHED TUMORS