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.

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.

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.

Inovação tecnológica e vantagem competitiva no setor de telefonia móvel

O setor de telefonia móvel tem passado por um processo de inovação tecnológica. Estas inovações afetam as estratégias das empresas do setor, e estabelecem uma forte concorrência entre elas. Sendo assim, a presente pesquisa objetiva identificar e comparar as vantagens competitivas que estão sendo geradas para as operadoras de telefonia móvel nacionais, tendo como objeto, analisar suas operações no Estado do Rio Grande do Sul, a partir da opção tecnológica (GSM ou CDMA) de cada uma. Para tanto, a pesquisa teve duas fases: na primeira fase, partiu-se de um referencial teórico inicial, sendo feita logo após uma pesquisa junto a quatorze (14) experts no setor de telefonia móvel, e com base na análise de conteúdo destas entrevistas acrescentaram-se outros referenciais teóricos para constituir o que é chamado aqui de arcabouço teórico (tendo como principais eixos teóricos os temas Inovação Tecnológica, Estratégias Competitivas e Teoria dos Stakeholders) das principais categorias estratégicas do setor de telefonia móvel brasileiro; na segunda fase, a partir do arcabouço teórico construído na primeira fase, foram feitos dois estudos de caso (Empresa A e Empresa B), com operadoras de Telefonia Móvel de atuação nacional, que representam juntas 67% do market share nacional, tendo como objeto de análise suas operações no Estado do Rio Grande do Sul (uma que optou pela tecnologia GSM e outra que optou pela tecnologia CDMA). Para análise desta segunda fase foi utilizada a técnica de triangulação de dados aliada ao método descritivo-interpretativo, onde foram analisadas seis (6) entrevistas em cada uma das empresas estudadas, os dados secundário s coletados, e as observações realizadas nas próprias empresas e em uma feira de telefonia móvel nacional. Como resultados são apresentados três (3) tipos de vantagens competitivas para cada uma das duas empresas: gerais; derivadas da opção tecnológica (CDMA; GSM); derivadas da organização. Neste sentido destaca-se que foram encontradas em sua maioria vantagens competitivas que advêm da opção tecnológica que cada empresa realizou, ou seja, foi possível, qualitativamente, identificar uma relação onde as inovações tecnológicas (CDMA; GSM) conduziram a atributos de vantagem competitiva. Por fim é feita uma comparação entre as vantagens competitivas identificadas para cada uma das empresas, à luz de um referencial teórico, que permitiu distinguir os recursos, as capacidades e as competências de cada uma. Nesta comparação foram identificadas do ponto de vista teórico, dois tipos de vantagens competitivas para a Empresa A (Capacidade Posicional e Interação Estratégia e Tecnologia) e dois tipos de vantagens competitivas para a Empresa B (Controle de Custos e Interação Estratégia e Tecnologia), ressaltando-se que também na comparação, as vantagens competitivas encontradas, derivaram diretamente da opção tecnológica de cada empresa.

Uma ferramenta de gestão em apoio a negociações complexas no setor brasileiro de telecomunicações

O propósito deste Estudo de Caso é descrever, comparar e interpretar informações que nos permita confirmar a importância da utilização de uma ferramenta de gestão durante os processos de negociação. Com a ajuda destas ferramentas, negociadores poderão maximizar as probabilidades de sucesso em suas negociações, dada a visão estratégica que estas oferecem nos estágios de preparação, desenvolvimento e conclusão das negociações. Quando utilizada adequadamente, a ferramenta dará aos negociadores uma visão mais ampla em cada etapa, muito além de somente pontos técnicos e/ou comerciais inerentes a um determinado projeto, os quais comumente são considerados. Para suportar este Estudo de Caso, foi realizada uma Pesquisa Qualitativa junto a profissionais de vendas de várias Empresas do Setor de Telcomunicações no Brasil, a qual vem apoiada por material teórico de autores de referência, objetivando confortar a percepção limitada pelas próprias características da pesquisa qualitativa. Este estudo avalia, diagnostica e recomenda soluções de gestão de negociações, à luz da técnica da criação de consensos suportadas e conduzidas pela ferramenta MNC (Matriz de Negociações Complexas), tendo como base os resultados finais de uma negociação comercial ocorrida em finais de 2003 entre duas grandes multinacionais do Setor de Telecomunicações e cujo principal objetivo na época era a obtenção de um contrato para expansão e modernização de uma Rede CDMA WLL de Telefonia Fixa Celular pertencente a uma Operadora. No decorrer da negociação a qual é abordada como exemplo, não foram utilizadas técnicas semelhantes àquelas sustentadas pela MNC, importante ferramenta de gestão de negociação, a qual já vem sendo utilizada inclusive pelo CDES (Conselho de Desenvolvimento Econômico e Social) do Brasil, nem tampouco nenhuma outra ferramenta de gestão. Este trabalho objetiva demonstrar que sua aplicação na organização, acompanhamento, diagnose, condução e conclusão de negociações, quaisquer que sejam estas, pode aumentar a probabilidade de êxito, trazendo para as Organizações, Instituições ou para aqueles que a adotarem, maior eficácia na condução e alcance dos resultados finais almejados. É apresentada uma análise diagnóstica dos parâmetros envolvidos na negociação em questão, passando por aqueles que estavam em desacordo com a ferramenta como o Contexto, as Opções, a Comunicação, o Relacionamento, as Concessões, o Facilitador, etc., e que foram considerados inconsistentes ou que eventualmente tenham passado despercebidos pelos negociadores, apresentando como conclusão os resultados comparativos entre a negociação utilizando-se os parâmetros da MNC e aqueles obtidos sem a utilização dos mesmos. Este estudo procura sustentar que a adoção desta ferramenta possui grande importância para a melhoria de desempenho durante os processos de negociação, não significando todavia, uma garantia de êxito sobre todas as negociações nas quais os negociadores estiverem envolvidos. Autores como Roger Fisher e Willian Ury (1981) sustentam que as pessoas negociam para obter um resultado melhor do que o que obteriam caso não negociassem. Desta forma, pode-se notar que de maneira direta ou indireta, no decorrer de nossas vidas sempre estivemos e a cada dia novamente estaremos nos deparando com a necessidade em participar de algum novo processo de negociação, diariamente, desde o mais básico ao mais complexo. A negociação passa a ser para o indivíduo uma ciência extremamente necessária e ao mesmo tempo complexa, atraente e sedutora, cuja percepção da necessidade de desenvolvimento dessas habilidades pode muitas vezes passar despercebida por muitos no transcorrer de suas vidas. As conclusões deste estudo de caso têm a intenção de demonstrar também que o sucesso de uma negociação nem sempre se resumirá em atingir os objetivos inicialmente propostos na MNC. Outros aspectos considerados por esta metodologia, se melhor ou pior aplicados, também poderão contribuir para o eventual sucesso ou fracasso de uma negociação.

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

Role of Locus coeruleus noradrenergic neurons in cardiorespiratory and thermal control during hypoxia

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Role of neurokinin-1 expressing neurons in the locus coeruleus on ventilatory and cardiovascular responses to hypercapnia

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Cardiovascular changes under normoxic and hypoxic conditions in the air-breathing teleost Synbranchus marmoratus: importance of the venous system

Synbranchus marmoratus is a facultative air-breathing fish, which uses its buccal cavity as well as its gills for air-breathing. S. marmoratus shows a very pronounced tachycardia when it surfaces to air-breathe. An elevation of heart rate decreases cardiac filling time and therefore may cause a decline in stroke volume (VS), but this can be compensated for by an increase in venous tone to maintain stroke volume. Thus, the study on S. marmoratus was undertaken to investigate how stroke volume and venous function are affected during air-breathing. To this end we measured cardiac output (Q), heart rate (fH), central venous blood pressure (PCV), mean circulatory filling pressure (MCFP), and dorsal aortic blood pressures (PDA) in S. marmoratus. Measurements were performed in aerated water (P-O2 > 130 mmHg), when the fish alternated between gill ventilation and prolonged periods of apnoeas, as well as during hypoxia (P-O2 <= 50 mmHg), when the fish changed from gill ventilation to air-breathing. Q increased significantly during gill ventilation compared to apnoea in aerated water through a significant increase in both fH and VS. PCV and MCFP also increased significantly. During hypoxia, when the animals surface to ventilate air, we found a marked rise in fH, PCV, MCFP, Q and VS, whereas PDA decreased significantly. Simultaneous increases in PCV and MCFP in aerated, as well as in hypoxic water, suggests that the venous system plays an important regulatory role for cardiac filling and VS in this species. In addition, we investigated adrenergic regulation of the venous system through bolus infusions of adrenergic agonists (adrenaline, phenylephrine and isoproterenol; 2 mu g kg(-1)). Adrenaline and phenylephrine caused a marked rise in PCV and MCFP, whereas isoproterenol led to a marked decrease in PCV, and tended to decrease MCFP. Thus, it is evident that stimulation of both alpha- and beta-adrenoreceptors affects venous tone in S. marmoratus.

The autonomic control and functional significance of the changes in heart rate associated with air breathing in the jeju, Hoplerythrinus unitaeniatus

The jeju is a teleost fish with bimodal respiration that utilizes a modified swim bladder as an air-breathing organ (ABO). Like all air-breathing fish studied to date, jeju exhibit pronounced changes in heart rate (f(H)) during air-breathing events, and it is believed that these may facilitate oxygen uptake (M-O2) from the ABO. The current study employed power spectral analysis (PSA) of f(H) patterns, coupled with instantaneous respirometry, to investigate the autonomic control of these phenomena and their functional significance for the efficacy of air breathing. The jeju obtained less than 5% of total M-O2 (M-tO2) from air breathing in normoxia at 26 degrees C, and PSA of beat-to-beat variability in fH revealed a pattern similar to that of unimodal water-breathing fish. In deep aquatic hypoxia (water P-O2=1 kPa) the jeju increased the frequency of air breathing (f(AB)) tenfold and maintained M-tO2 unchanged from normoxia. This was associated with a significant increase in heart rate variability (HRV), each air breath (AB) being preceded by a brief bradycardia and then followed by a brief tachycardia. These f(H) changes are qualitatively similar to those associated with breathing in unimodal air-breathing vertebrates. Within 20 heartbeats after the AB, however, a beat-to-beat variability in f(H) typical of water-breathing fish was re-established. Pharmacological blockade revealed that both adrenergic and cholinergic tone increased simultaneously prior to each AB, and then decreased after it. However, modulation of inhibitory cholinergic tone was responsible for the major proportion of HRV, including the precise beat-to-beat modulation of f(H) around each AB. Pharmacological blockade of all variations in f(H) associated with air breathing in deep hypoxia did not, however, have a significant effect upon f(AB) or the regulation of M-tO2. Thus, the functional significance of the profound HRV during air breathing remains a mystery.