Ferrocene in conjugation with a Fischer carbene: Synthesis, NLO, and electrochemical behavior of a novel organometallic push-pull system

Using an iterative sequence of Wittig olefination, reduction, oxidation, and condensation of an active methylene group to carbonyl, it was possible to prepare a series of organometallic push-pull molecules [(CO)(5)M=C(OCH3)(-CH=CH-)(n)(C5H4)Fe(C5H5), M = W, Cr, n = 1-4] in which ferrocene is the donor element and a Fisher carbene moeity is the acceptor group. The molecular first hyperpolarizability beta was determined by hyper-Rayleigh scattering experiments. The beta values ranged from 110 x 10(-30) to 2420 x 10(-30) esu in acetonitrile, and they are among the highest reported for organometallic molecules so far. Electrochemical measurements are consistent with the push-pull nature of these compounds.

Spiroacetals in the Colonization Behaviour of the Coffee Berry Borer: A 'Push-Pull' System

Coffee berries are known to release several volatile organic compounds, among which is the spiroacetal, conophthorin, an attractant for the coffee berry borer Hypothenemus hampei. Elucidating the effects of other spiroacetals released by coffee berries is critical to understanding their chemo-ecological roles in the host discrimination and colonization process of the coffee berry borer, and also for their potential use in the management of this pest. Here, we show that the coffee berry spiroacetals frontalin and 1,6-dioxaspiro [4.5] decane (referred thereafter as brocain), are also used as semiochemicals by the coffee berry borer for host colonization. Bioassays and chemical analyses showed that crowding coffee berry borers from 2 to 6 females per berry, reduced borer fecundity, which appeared to correlate with a decrease in the emission rates of conophthorin and frontalin over time. In contrast, the level of brocain did not vary significantly between borer-uninfested and infested berries. Brocain was attractive at lower doses, but repellent at higher doses while frontalin alone or in a blend was critical for avoidance. Field assays with a commercial attractant comprising a mixture of ethanol and methanol (1:1), combined with frontalin, confirmed the repellent effect of this compound by disrupting capture rates of H. hampei females by 77% in a coffee plantation. Overall, our results suggest that the levels of frontalin and conophthorin released by coffee berries determine the host colonization behaviour of H. hampei, possibly through a 'push-pull' system, whereby frontalin acts as the 'push' (repellent) and conophthorin acting as the 'pull' (attractant). Furthermore, our results reveal the potential use of frontalin as a repellent for management of this coffee pest.

Simulation-based comparison of pull-push system in motorcycle assembly line

To investigate the effects of adopting a pull system in assembly lines in contrast to a push system, simulation software called “ARENA” is used as a tool in order to present numerical results from both systems. Simulation scenarios are created to evaluate the effects of attributes changing in assembly systems, with influential factors including the change of manufacturing system (push system to pull system) and variation of demand. Moreover, pull system manufacturing consists of the addition attribute, which is the number of buffer storage. This paper will provide an analysis based on a previous case study, hence process time and workflow refer to the journal name “Optimising and simulating the assembly line balancing problem in a motorcycle manufacturing company: a case study” [2]. The implementation of the pull system mechanism is to produce a system improvement in terms of the number of Work-In-Process (WIP), total time of products in the system, and the number of finished product inventory, while retaining the same throughput.

Simulating the change from a push to pull production system

This paper will document the initial discrete-event simulation performed to study a proposed change from a push to a pull system in an existing manufacturing company. The system is characterised by five machine lines with intermediate buffers, and five major part groupings. A simulation model has been developed to mimic the flow of kanban cards in the physical system, by using a series of requests that propagate back through the facility, which the machines must respond to. The customer
demand therefore controls the level of activity in the plant. The results of the initial modelling steps will be presented in this paper, especially the impact of kanban lot size and demand variability on the output and stability of the production system, from which a set of future work is proposed.

Implementação da filosofia pull na produção na empresa Schnellecke

Trabalho Final de mestrado para obtenção do grau de Mestre em Engenharia Mecânica perfil Manutenção e Produção

Controlo e monitorização de um sistema de Auto-Pull

Esta dissertação descreve o estudo do controlo e da monitorização de um sistema de autopull, bem como o estudo da implementação de um destes sistemasnuma área de negócio. Inicialmente, de modo a percecionar as melhores opções a tomar para a realização deste projeto foram estudadas duas redes de comunicação locais, redes Ethernet e redes CAN, tendo-se optado pelas redes Ethernet, sendo as razões que determinaram esta escolha explanadas no desenvolvimento do relatório. Após ter sido selecionada a rede que foi utilizada, foram estudados os requisitos do sistema e procuradas no mercado soluções que os satisfaçam. Para a comunicação em tempo real foram utilizadas Web Sockets e para a utilização destas,foi necessário um servidor de Web Sockets, tendo a escolha recaídosobre onodejs. Posteriormente, foi elaborada uma interface gráfica que permitiu a criação de um sistema inteligente que auxilia os clientes do espaço a efetuarem pedidos bem como a chamarem os funcionários, não necessitando de passar os longos tempos de espera que normalmenteestão associados a estes espaços. Posto isto, foi realizado um website que deverá apresentar o espaço, os próximos eventos a realizar e outras informações importantes. Este sistema torna-se uma mais-valia para a divulgação da tecnologia implementada e para a divulgação dos espaços que eventualmente venham a adotar um sistema análogo. De seguida foi efetuado um plano de negócios, simulando um espaço físico que eventualmente implementasse esta tecnologia. Para tal, foi estudada a envolvente externa e interna em que este negócio estaria inserido, as políticas de marketing que deveriam ser seguidas e ainda um plano financeiro que descrevesse o investimento, as vendas esperadas e todos os restantes componentes económicos do projeto. Por último foram tecidas as principais conclusões inerentes ao projeto desenvolvido e analisadas as possibilidades de melhorias futuras.

Desperdícios na cadeia logística no âmbito industrial

Projecto apresentado ao Instituto Politécnico do Porto para obtenção do Grau de Mestre em Logística Orientada por Prof. Doutor Gouveia

5-(1-(4-phenyl)-3-(4-nitrophenyl)triazene)-10,15,20-triphenylporphyrin: a new triazene-porphyrin dye and its spectroelectrochemical properties

The new triazene-porphyrin dye 5-(1-(4-phenyl)-3-(4-nitrophenyl)triazene)-10,15,20-triphenylporphyrin, encompassing a reactive protonated triazene moiety, was prepared starting from meso-tetraphenylporphyrin (H2TPP), first converting it to the 5-(4-nitrophenyl)-10,15,20-triphenylporphyrin, then reducing to the 5-(4-aminophenyl)-10,15,20-tri(phenyl) porphyrin intermediate, and reacting with the diazonium salt of 4-nitroaniline; and characterized by spectroscopic and electrochemical methods. The absorption spectrum of the neutral species resembled the sum of H2TPP and of 1,3-bis(4-nitrophenyl) triazene spectrum, but the deprotonated anionic species showed more delocalized frontier orbitals, behaving as a push-pull system exhibiting triazenide-to-porphyrin charge-transfer transitions.

Ferramentas Lean na indústria corticeira

O presente projeto tem como objetivo a aplicação de ferramentas do universo Lean Thinking na indústria corticeira de forma a identificar e eliminar fontes de desperdício, criar valor e envolver a organização numa cultura de melhoria contínua focada na satisfação do cliente. A Unidade Industrial de Lamas encontra-se a passar por uma fase de mudança e carece da aplicação de ferramentas 5S, Gestão Visual, Kaizen Diário e Standard Work, contempladas no seu programa de melhoria contínua intitulado de Cork.MAIS. A aplicação das ferramentas comprovam o sucesso em termos de qualidade e eficiência operacional. Os 5S conduzem à eficiência, segurança e organização dos postos de trabalho e quando implementados despoletam de forma natural a necessidade de implementação da ferramenta Gestão Visual que acarreta inúmeros benefícios visto que visa sistemas simples e intuitivos. A ferramenta Kaizen Diário contribuiu para aumentar a comunicação entre os diferentes turnos, alinhar os colaboradores com a estratégia da Unidade Industrial de Lamas e identificar oportunidades de melhoria fomentando o trabalho em equipa. A ferramenta Standard Work contribuiu para a redução dos encravamentos dos equipamentos SVE obtendo-se um aumento de 11% do Overall Equipment Effectiveness. Realizar uma retrospetiva de todos os processos e fluxos de produção tornou-se oportuno e, para tal, recorreu-se à ferramenta Value Stream Mapping. Todo o trabalho em equipa serviria para analisar o estado atual da cadeia de valor da Unidade Industrial de Lamas no que respeita ao planeamento e fluxos de material e informação, metodologia do controlo de produto e processo e eficiência operacional. Todas as oportunidades de melhoria identificadas e implementadas acrescentam valor à cadeia da organização mas dá-se destaque às ações de melhoria implementadas no âmbito do projeto de planeamento e fluxos de informação e material. Todas as novas ferramentas implementadas contempladas no sistema pull da organização conduziram a uma redução de 11% do material em work in process e um aumento de 25% da taxa de satisfação de encomendas.

Application of co-operative agents in handling fluctuations in a pull production system

This paper presents the general details of the structure and strategy of a multi-agent system that is being developed to improve the performance of pull (kanban) production control to handle large fluctuations in product demand. Employing a set of generic, heterarchial agents each controlling a single product and co-operating together to ensure that all components, regardless of demand fluctuation, are manufactured on time as per basic kanban principles. Preliminary results indicate that the basic kanban model does not cater for large demand fluctuations and the application of this multi-agent strategy may be beneficial to improving the overall system performance and increase the likelihood that all products will be manufactured on time.

Towards a global carbon integrity system : learning from the GFC and avoiding a GCC

This paper examines some of the central global ethical and governance challenges of climate change and carbon emis-sions reduction in relation to globalization, the “global financial crisis” (GFC), and unsustainable conceptions of the “good life”, and argues in favour of the development of a global carbon “integrity system”. It is argued that a funda-mental driver of our climate problems is the incipient spread of an unsustainable Western version of the “good life”, where resource-intensive, high-carbon western lifestyles, although frequently criticized as unsustainable and deeply unsatisfying, appear to have established an unearned ethical legitimacy. While the ultimate solution to climate change is the development of low carbon lifestyles, the paper argues that it is also important that economic incentives support and stimulate that search: the sustainable versions of the good life provide an ethical pull, whilst the incentives provide an economic push. Yet, if we are going to secure sustainable low carbon lifestyles, it is argued, we need more than the ethical pull and the economic push. Each needs to be institutionalized—built into the governance of global, regional, national, sub-regional, corporate and professional institutions. Where currently weakness in each exacerbates the weaknesses in others, it is argued that governance reform is required in all areas supporting sustainable, low carbon versions of the good life.

Crystal Structure, Ultraviolet Spectrum, and Electronic Structure of a Strongly Twisted Push-Pull Ethylene, approaching an Amidinium-Vinylogous Dithioate Zwitterion

The crystal structure of 1,3-di benzyl -2 - (4,4-dimet hyl- 2,5- bist hioxocyclo hexylidene) imidazolidine (2) shows a twist of 80.8(5)' about the inter-ring bond, which has a length of 1.482(6) A. The near orthogonality of the donor and acceptor parts of this formal push-pull ethylene makes the structure approach that of a zwitterion, as evidenced by bond lengths indicating strong electron delocalization. The acceptor part approaches a vinylogous dithioate structure, the donor part an amidinium system. The U.V. spectrum shows an n + R and a R + R transition, at 51 1 and 41 7.5 nm, respectively; according to CNDO/S calculations these are located entirely in the [S-C-C-C-SI- part. Two bands at shorter wavelength are ascribed to transitions from combinations of the lone-pair orbitals on the sulphur atoms to a n* orbital in the [N-C-N] + part; this is facilitated by the near perpendicularity of the two parts of the molecule.

Real-time density matrix renormalization group dynamics of spin and charge transport in push-pull polyenes and related systems

In this paper we investigate the effect of terminal substituents on the dynamics of spin and charge transport in donor-acceptor substituted polyenes [D-(CH)(x)-A] chains, also known as push-pull polyenes. We employ a long-range correlated model Hamiltonian for the D-(CH)(x)-A system, and time-dependent density matrix renormalization group technique for time propagating the wave packet obtained by injecting a hole at a terminal site, in the ground state of the system. Our studies reveal that the end groups do not affect spin and charge velocities in any significant way, but change the amount of charge transported. We have compared these push-pull systems with donor-acceptor substituted polymethine imine (PMI), D-(CHN)(x)-A, systems in which besides electron affinities, the nature of p(z) orbitals in conjugation also alternate from site to site. We note that spin and charge dynamics in the PMIs are very different from that observed in the case of push-pull polyenes, and within the time scale of our studies, transport of spin and charge leads to the formation of a ``quasi-static'' state.

Snap-through and pull-in instabilities of an arch-shaped beam under an electrostatic loading

The snap-through and pull-in instabilities of the micromachined arch-shaped beams under an electrostatic loading are studied both theoretically and experimentally. The pull-in instability that results in a system collision with an electrode substrate may lead to a system failure and, thus, limits the system maximum displacement. The beam/plate structure with a flat initial configuration under an electrostatic loading can only experience the pull-in instability. With the different arch configurations, the structure may experience either only the pull-in instability or the snap-through and pull-in instabilities together. As shown in our computation and experiment, those arch-shaped beams with the snap-through instability have the larger maximum displacement compared with the arch-shaped beams with only the pull-in stability and those with the flat initial configuration. The snap-through occurs by exerting a fixed load, and the structure experiences a discontinuous displacement jump without consuming power. Furthermore, after the snap-through jump, the structures are demonstrated to have the capacity to withstand further electrostatic loading without pull-in. Those properties of consuming no power and increasing the structure deflection range without pull-in is very useful in microelectromechanical systems design, which can offer better sensitivity and tuning range.