Direct probing of photoinduced electron transfer in a self- assembled biomimetic [2Fe2S]-hydrogenase complex using ultrafast vibrational spectroscopy

A pyridyl-functionalized diiron dithiolate complex, [μ-(4-pyCH2−NMI-S2)Fe2(CO)6] (3, py = pyridine(ligand), NMI = naphthalene monoimide) was synthesized and fully characterized. In the presence of zinc tetraphenylporphyrin (ZnTPP), a self-assembled 3·ZnTPP complex was readily formed in CH2Cl2 by the coordination of the pyridyl nitrogen to the porphyrin zinc center. Ultrafast photoinduced electron transfer from excited ZnTPP to complex 3 in the supramolecular assembly was observed in real time by monitoring the ν(CO) and ν(CO)NMI spectral changes with femtosecond time-resolved infrared (TRIR) spectroscopy. We have confirmed that photoinduced charge separation produced the monoreduced species by comparing the time-resolved IR spectra with the conventional IR spectra of 3•− generated by reversible electrochemical reduction. The lifetimes for the charge separation and charge recombination processes were found to be τCS = 40 ± 3 ps and τCR = 205 ± 14 ps, respectively. The charge recombination is much slower than that in an analogous covalent complex, demonstrating the potential of a supramolecular approach to extend the lifetime of the chargeseparated state in photocatalytic complexes. The observed vibrational frequency shifts provide a very sensitive probe of the delocalization of the electron-spin density over the different parts of the Fe2S2 complex. The TR and spectro-electrochemical IR spectra, electron paramagnetic resonance spectra, and density functional theory calculations all show that the spin density in 3•− is delocalized over the diiron core and the NMI bridge. This delocalization explains why the complex exhibits low catalytic dihydrogen production even though it features a very efficient photoinduced electron transfer. The ultrafast porphyrin-to-NMIS2−Fe2(CO)6 photoinduced electron transfer is the first reported example of a supramolecular Fe2S2-hydrogenase model studied by femtosecond TRIR spectroscopy. Our results show that TRIR spectroscopy is a powerful tool to investigate photoinduced electron transfer in potential dihydrogen-producing catalytic complexes, and that way to optimize their performance by rational approaches.

[M(CO)4(2,2′-bipyridine)] (M = Cr, Mo, W) as efficient catalysts for electrochemical reduction of CO2 to CO at a gold electrode

Group 6 complexes of the type [M(CO)4(bpy)] (M=Cr, Mo, W) are capable of behaving as electrochemical catalysts for the reduction of CO2 at potentials less negative than those for the reduction of the radical anions [M(CO)4(bpy)].−. Cyclic voltammetric, chronoamperometric and UV/Vis/IR spectro-electrochemical data reveal that five-coordinate [M(CO)3(bpy)]2− are the active catalysts. The catalytic conversion is significantly more efficient in N-methyl-2-pyrrolidone (NMP) compared to tetrahydrofuran, which may reflect easier CO dissociation from 1e−-reduced [M(CO)4(bpy)].− in the former solvent, followed by second electron transfer. The catalytic cycle may also involve [M(CO)4(H-bpy)]− formed by protonation of [M(CO)3(bpy)]2−, especially in NMP. The strongly enhanced catalysis using an Au working electrode is remarkable, suggesting that surface interactions may play an important role, too.

The chaotic frequency hopping signals for MIMO radar

In multiple-input multiple-output (MIMO) radar systems, the transmitters emit orthogonal waveforms to increase the spatial resolution. New frequency hopping (FH) codes based on chaotic sequences are proposed. The chaotic sequences have the characteristics of good encryption, anti-jamming properties and anti-intercept capabilities. The main idea of chaotic FH is based on queuing theory. According to the sensitivity to initial condition, these sequences can achieve good Hamming auto-correlation while also preserving good average correlation. Simulation results show that the proposed FH signals can achieve lower autocorrelation side lobe level and peak cross-correlation level with the increasing of iterations. Compared to the LFM signals, this sequence has higher range-doppler resolution.

Negotiating the British landscape

According to many accounts, a key paradigm for understanding art in Post WWII Britain is one of Englishness versus internationalism or abstraction versus realism . These terms have a rich inflection of meanings that have been subject to interrogation over the last few decades. Anwar Shemza came to Britain and practiced his art at a time when these competing claims were at their height. In a postcolonial reading entitled “Black Diaspora Artists in Britain: Three ‘Moments’ in Post-War Britain” Stuart Hall recently used David Scott’s framework of a ‘problem space’, that is discursively defined through questions, tensions and conjunctures, that couched the entry of what he describes as first waive British commonwealth artists into critical visibility in Britain. This can be characterized in part by the reviews of WG Archer and GM Butcher, both supporters of Shemza and prominent critics of the period. Hall includes Shemza in this framework that defines the work and his aspirations as constituted through the tensions of what was perceived to be anti-colonialist aims of modernism through universalism and the ‘nativist’ current in anti-colonial nationalism . This text will focus particularly on the problematic of Landscape as a ‘problem space’ of vernacular and modernism, over here and over there. The aim is not to define Shemza within the tradition of English landscape nor to exclude him but to position him within a discursive field of landscape and modernism in mid twentieth Century art.

Investigating subtypes of reward processing deficits as trait markers for depression

Background: Anhedonia, the loss of pleasure in usually enjoyable activities, is a central feature of major depressive disorder (MDD). The aim of the present study was to examine whether young people at a familial risk of depression display signs of anticipatory, motivational or consummatory anhedonia, which would indicate that these deficits may be trait markers for MDD. Methods: The study was completed by 22 participants with a family history of depression (FH+) and 21 controls (HC). Anticipatory anhedonia was assessed by asking participants to rate their anticipated liking of pleasant and unpleasant foods which they imagined tasting when cued with images of the foods. Motivational anhedonia was measured by requiring participants to perform key presses to obtain pleasant chocolate taste rewards or to avoid unpleasant apple tastes. Additionally, physical consummatory anhedonia was examined by instructing participants to rate the pleasantness of the acquired tastes. Moreover, social consummatory anhedonia was investigated by asking participants to make preference-based choices between neutral facial expressions, genuine smiles, and polite smiles. Results: It was found that the FH+ group’s anticipated liking of unpleasant foods was significantly lower than that of the control group. By contrast, no group differences in the pleasantness ratings of the actually experienced tastes or in the amount of performed key presses were observed. However, controls preferred genuine smiles over neutral expressions more often than they preferred polite smiles over neutral expressions, while this pattern was not seen in the FH+ group. Conclusion: These findings suggest that FH+ individuals demonstrate an altered anticipatory response to negative stimuli and show signs of social consummatory anhedonia, which may be trait markers for depression.

Elucidating the structure of chiral molecules by using amplified vibrational circular dichroism: from theory to experimental realization

Recent experimental observations of enhanced vibrational circular dichroism (VCD) in molecular systems with low-lying electronically excited states suggest interesting new applications of VCD spectroscopy. The theory describing VCD enhancement through vibronic coupling schemes was derived by Nafie in 1983, but only recently experimental evidence of VCD amplification has demonstrated the extent to which this effect can be exploited as a structure elucidation tool to probe local structure. In this Concept paper, we give an overview of the physics behind vibrational circular dichroism, in particular the equations governing the VCD amplification effect, and review the latest experimental developments with a prospective view on the application of amplified VCD to locally probe biomolecular structure.

A reappraisal of Baskerville's Greek types

Ιn the eighteenth century the printing of Greek texts continued to be central to scholarship and discourse. The typography of Greek texts could be characterised as a continuation of French models from the sixteenth century, with a gradual dilution of the complexity of ligatures and abbreviations, mostly through printers in the Low Countries. In Britain, Greek printing was dominated by the university presses, which reproduced conservatively the continental models – exemplified by Oxford's Fell types, which were Dutch adaptations of earlier French models. Hindsight allows us to identify a meaningful development in the Greek types cut by Alexander Wilson for the Foulis Press in Glasgow, but we can argue that in the middle of the eighteenth century Baskerville was considering Greek printing the typographic environment was ripe for a new style of Greek types. The opportunity to cut the types for a New Testament (in an twin edition that included a generous octavo and a large quarto version) would seem perfect for showcasing Baskerville's capacity for innovation. His Greek type maintained the cursive ductus of earlier models, but abandoned complex ligatures and any hint of scribal flourish. He homogenised the modulation of the letter strokes and the treatment of terminals, and normalised the horizontal alignments of all letters. Although the strokes are in some letters too delicate, the narrow set of the style composes a consistent, uniform texture that is a clean break from contemporaneous models. The argument is made that this is the first Greek typeface that can be described as fully typographic in the context of the technology of the time. It sets a pattern that was to be followed, without acknowledgement, by Richard Porson nearly a century and a half later. The typeface received little praise by typographic historians, and was condemned by Victor Scholderer in his retrospective of Greek typography. A survey of typeface reviews in the surrounding decades establishes that the commentators were mostly reproducing the views of an arbitrary typographic orthodoxy, for which only types with direct references to Renaissance models were acceptable. In these comments we detect a bias against someone considered an arriviste in the scholarly printing establishment, as well as a conservative attitude to typographic innovation.

Genomic evidence for the Pleistocene and recent population history of Native Americans

How and when the Americas were populated remains contentious. Using ancient and modern genome-wide data, we found that the ancestors of all present-day Native Americans, including Athabascans and Amerindians, entered the Americas as a single migration wave from Siberia no earlier than 23 thousand years ago (ka) and after no more than an 8000-year isolation period in Beringia. After their arrival to the Americas, ancestral Native Americans diversified into two basal genetic branches around 13 ka, one that is now dispersed across North and South America and the other restricted to North America. Subsequent gene flow resulted in some Native Americans sharing ancestry with present-day East Asians (including Siberians) and, more distantly, Australo-Melanesians. Putative “Paleoamerican” relict populations, including the historical Mexican Pericúes and South American Fuego-Patagonians, are not directly related to modern Australo-Melanesians as suggested by the Paleoamerican Model.

Neural signals of “Intensity” but not “Wanting” or “Liking” of rewards may be trait markers for depression

We have shown previously that particpants “at risk” of depression have decreased neural processing of reward suggesting this might be a neural biomarker for depression. However, how the neural signal related to subjective experiences of reward (wanting, liking, intensity) might differ as trait markers for depression, is as yet unknown. Using SPM8 parametric modulation analysis the neural signal related to the subjective report of wanting, liking and intensity was compared between 25 young people with a biological parent with depression (FH) and 25 age/gender matched controls. In a second study the neural signal related to the subjective report of wanting, liking and intensity was compared between 13 unmedicated recovered depressed (RD) patients and 14 healthy age/gender matched controls. The analysis revealed differences in the neural signal for wanting, liking and intensity ratings in the ventral striatum, dmPFC and caudate respectively in the RD group compared to controls . Despite no differences in the FH groups neural signal for wanting and liking there was a difference in the neural signal for intensity ratings in the dACC and anterior insula compared to controls. These results suggest that the neural substrates tracking the intensity but not the wanting or liking for rewards and punishers might be a trait marker for depression.

Deficiency of the human complement regulatory protein factor H associated with low levels of component C9

We identified a 4-year-old Brazilian boy from a family of Japanese descent and history of consanguinity, who suffered from severe recurrent pneumonia. He carries factor H (FH) deficiency associated with reduced levels of component C9 and low serum levels of C3 and factor B. His mother also presented low levels of these proteins and factor I, while his father and sister had only lower levels of FH. Western blot assays confirmed the complete absence of FH and FHL-1 polypeptides in this patient. Sequencing of the proband`s FH cDNA revealed a homozygous G453A substitution, encoding an Arg(127)His change. His mother, father and sister are heterozygous for this substitution. Despite the absence of FH in the plasma, this protein was detected in the patient`s fibroblasts, suggesting that Arg(127) may be important for FH secretion. Low concentrations of C9 were detected in the proband serum but no mutations in the patient`s C9 gene or promoter have been identified, suggesting that this is a consequence of uncontrolled complement activation and high C9 consumption.

1988 Yearbook

Vol. 7; Sept. 1988; 109 p. b&w, color photographs TOC: Life at LaGuardia…2 / Activities and Events…17 / Faculty and Staff…33 / Activities at LaGuardia…49 / Graduation…71 Yearbook Committee Credits: Faculty Advisor, Vincent Banrey; Project Director, Catherine Whan; Editors: Alexandra Gomez, Juan Jimenez, GloryAnn Torres; Asst. Editor, Kenny Rosa; LAYOUT: Vincent Banrey, Marino "Tito" Cabrera, Shirley Chance, George Condors, Milton Ferreira, Maria Flores, Alexandra Gomez, Ana Lisa Gonzalez, Bernadette Henry, Juan Jimenez, Alejandro Meneses, Richard Provost, Kenny Rosa, Maria Sanchez, GloryAnn Torres, Catherine Whan, Alan O. Young; PHOTOGRAPHY: Peter Abbate, Sandra Acres, Young Baek Choi, Randy Fader Smith, Milton Ferriera, Alexandra Gomez, Juan Jimenez, Seymour Lerman, Chuck Lindsey, Victoria Pamias, Richard Provost, Alan Scribner, Frank Tocco, GloryAnn Torres, Catherine Whan. ART: Jose Marti (Cover Design and Division Pages); Martin Carrichner, Jose Marti (Endsheet Design), Arnold Escalera, Jacqui Fernandez, Richard Massey, Alejandro Meneses; WRITING: Anthony Archer, Alexandra Bastidas, Joie Fadde, Alexandra Gomez, Ana Lisa Gonzalez, Doreen Hansen, Bernadette Henry, Sarah Hudson, Juan Jimenez, Donna Libert, Cathy Passiglia, Jody Pincus, Richard Provost, Kenny Rosa, Maria Sanchez, Alan Scribner, Christiana Sommerville, GloryAnn Torres, Catherine Whan, Alan O. Young; SPECIAL THANKS: Blanca Arbito, Classic Studios, Edward Hollins, Umoja Kwanguvu, Kelly Johnson and the LaGuardia Archives, Andrew Saluga and Recreation Staff, Ted Schiffman of Taylor Publishing.

Half-sib progenies evaluation in velvet grass

O capim-lanudo (Holcus lanatus L.) possui grande potencial de utilização como pastagem de inverno nas regiões subtropicais, devido a seu bom estabelecimento, persistência, produção, resistência ao frio, palatabilidade e capacidade de afilhamento. O objetivo deste trabalho foi estimar a variabilidade genética e a herdabilidade de caracteres agronômicos e identificar progênies superiores. Foram avaliadas 60 progênies de meios-irmãos, para altura (NH) e diâmetro da planta na fase vegetativa, duração do ciclo vegetativo (ciclo), altura final (FH) e número de afilhos. Houve diferença entre progênies para todos os caracteres. As estimativas de herdabilidade foram de 38%, 32%, 92%, 57% e 64% para NH, diâmetro, ciclo, FH e afilhos, respectivamente. O maior ganho genético estimado foi de 30,77 % para o número de afilhos. Existe variabilidade para todos os caracteres e são esperados ganhos na seleção entre progênies.

Emprego de redes neurais artificiais supervisionadas e não supervisionadas no estudo de parâmetros reológicos de excipientes farmacêuticos sólidos

In this paper artificial neural network (ANN) based on supervised and unsupervised algorithms were investigated for use in the study of rheological parameters of solid pharmaceutical excipients, in order to develop computational tools for manufacturing solid dosage forms. Among four supervised neural networks investigated, the best learning performance was achieved by a feedfoward multilayer perceptron whose architectures was composed by eight neurons in the input layer, sixteen neurons in the hidden layer and one neuron in the output layer. Learning and predictive performance relative to repose angle was poor while to Carr index and Hausner ratio (CI and HR, respectively) showed very good fitting capacity and learning, therefore HR and CI were considered suitable descriptors for the next stage of development of supervised ANNs. Clustering capacity was evaluated for five unsupervised strategies. Network based on purely unsupervised competitive strategies, classic "Winner-Take-All", "Frequency-Sensitive Competitive Learning" and "Rival-Penalize Competitive Learning" (WTA, FSCL and RPCL, respectively) were able to perform clustering from database, however this classification was very poor, showing severe classification errors by grouping data with conflicting properties into the same cluster or even the same neuron. On the other hand it could not be established what was the criteria adopted by the neural network for those clustering. Self-Organizing Maps (SOM) and Neural Gas (NG) networks showed better clustering capacity. Both have recognized the two major groupings of data corresponding to lactose (LAC) and cellulose (CEL). However, SOM showed some errors in classify data from minority excipients, magnesium stearate (EMG) , talc (TLC) and attapulgite (ATP). NG network in turn performed a very consistent classification of data and solve the misclassification of SOM, being the most appropriate network for classifying data of the study. The use of NG network in pharmaceutical technology was still unpublished. NG therefore has great potential for use in the development of software for use in automated classification systems of pharmaceutical powders and as a new tool for mining and clustering data in drug development