Metallacyclocumulenes: A Theoretical Perspective on the Structure, Bonding, and Reactivity

CONSPECTUS: Transition metals help to stabilize highly strained organic fragments. Metallacycles, especially unsaturated ones, provide much variety in this area. We had a sustained interest in understanding new C-C bond formation reactions affected by binuclear transition metal fragments Cp2M. One such study led to the exploration of the bimetallic C-C cleavage and coupled complexes, where the acetylide ligands bridge two metal atoms. The underlying M-C interaction in these complexes inspired the synthesis of a five-membered cyclocumulene complex, which opened a new phase in organometallic chemistry. The metallacyclocumulene produces a variety of C-C cleavage and coupled products including a radialene complex. Group 4 metallocenes have thus unlocked a fascinating chemistry by stabilizing strained unsaturated C4 organic fragments in the form of five-membered metallacyclocumulenes, metallacyclopentynes, and metallacycloallenes. Over the years, we have carried out a comprehensive theoretical study to understand the unusual stability and reactivity of these metallacycles. The unique (M-C-beta) interaction of the internal carbon atoms with the metal atom is the reason for unusual stability of the metallacycles. We have also shown that there is a definite dependence of the C-C coupling and cleavage reactions on the metal of metallacyclocumulenes. It demonstrates unexpected reaction pathways for these reactions. Based on this understanding, we have predicted and unraveled the stabilization factors of an unusual four-membered metallacycloallene complex. Indeed, our prediction about a four-membered heterometallacycle has led to an interesting bonding situation, which is experimentally realized. This type of M-C bonding is intriguing from a fundamental perspective and has great relevance in synthesizing unusual structures with interesting properties. In this Account, we first give a short prologue of what led to the present study and describe the salient features of the structure and bonding of the metallacyclocumulenes. The unusual reaction pathway of this metallacycle is explored next. Similar features of the metallacyclopentynes and metallacycloallenes are briefly mentioned. Then, we discuss the exploitation of the unique M-C bonding to design some exotic molecules such as a four-membered metallacycloallene complex. Our efforts to build a conceptual framework to understand these metallacycles and to exploit their chemistry continue.

Efficacious Gene Silencing in Serum and Significant Apoptotic Activity Induction by Survivin Downregulation Mediated by New Cationic Gemini Tocopheryl Lipids

Nonviral gene delivery offers cationic liposomes as promising instruments for the delivery of double-stranded RNA (ds RNA) molecules for successful sequence-specific gene silencing (RNA interference). The efficient delivery of siRNA (small interfering RNA) to cells while avoiding unexpected side effects is an important prerequisite for the exploitation of the power of this excellent tool. We present here six new tocopherol based cationic gemini lipids, which induce substantial gene knockdown without any obvious cytotoxicity. All the efficient coliposomal formulations derived from each of these geminis and a helper lipid, dioleoylphosphatidylethanolamine (DOPE), were well characterized using physical methods such as atomic force microscopy (AFM) and dynamic light scattering (DLS). Zeta potential measurements were conducted to estimate the surface charge of these formulations. Flow cytometric analysis showed that the optimized coliposomal formulations could transfect anti-GFP siRNA efficiently in three different GFP expressing cell lines, viz., HEK 293T, HeLa, and Caco-2, significantly better than a potent commercial standard Lipofectamine 2000 (L2K) both in the absence and in the presence of serum (FBS). Notably, the knockdown activity of coliposomes of gemini lipids was not affected even in the presence of serum (10% and 50% FBS) while it dropped down for L2K significantly. Observations under a fluorescence microscope, RT-PCR, and Western blot analysis substantiated the flow cytometry results. The efficient cellular entry of labeled siRNA in GFP expressing cells as evidenced from confocal microscopy put forward these gemini lipids among the potent lipidic carriers for siRNA. The efficient transfection capabilities were also profiled in a more relevant fashion while performing siRNA transfections against survivin (an anti-apoptotic protein) which induced substantial apoptosis. Furthermore, the survivin downregulation improved the therapeutic efficacy levels of an anticancer drug, doxorubicin, significantly. In short, the new tocopherol based gemini lipids appear to be highly promising for achieving siRNA mediated gene knockdown in various cell lines.

Synthesis of Instruction Extensions on HyperCell, a Reconfigurable Datapath

In this paper we present HyperCell as a reconfigurable datapath for Instruction Extensions (IEs). HyperCell comprises an array of compute units laid over a switch network. We present an IE synthesis methodology that enables post-silicon realization of IE datapaths on HyperCell. The synthesis methodology optimally exploits hardware resources in HyperCell to enable software pipelined execution of IEs. Exploitation of temporal reuse of data in HyperCell results in significant reduction of input/output bandwidth requirements of HyperCell.

A Dynamic Loading Device for Suction Foundations in Centrifuge Modeling

Suction bucket foundations are widely used in the offshore platform for the exploitation of the offshore petroleum and natural gas resources. During winter seasons, ice sheets formed in Bohai Bay will impose strong impact and result in strong vibration on the platform. This paper describes a dynamic loading device developed on the geotechnical centrifuge and its application in modeling suction bucket foundation under the equivalent ice-induced vibration loadings. Some experimental results are presented. It is shown that when the loading amplitude is over a critical value, the sand at the upper part around the bucket softens or even liquefies. The excess pore pressure decreases from the upper part to the lower part of the sand foundation in vertical direction while decreases from near to far away from the bucket's side wall in the horizontal direction. Large settlements of the bucket and the sand around the bucket occur under the horizontal dynamic loading. The dynamic responses of the bucket with smaller size are heavier.

Simulating dynamic covariance structures for testing the adaptive behavior of variable selection algorithms (Invited Paper)

Variable selection for regression is a classical statistical problem, motivated by concerns that too large a number of covariates may bring about overfitting and unnecessarily high measurement costs. Novel difficulties arise in streaming contexts, where the correlation structure of the process may be drifting, in which case it must be constantly tracked so that selections may be revised accordingly. A particularly interesting phenomenon is that non-selected covariates become missing variables, inducing bias on subsequent decisions. This raises an intricate exploration-exploitation tradeoff, whose dependence on the covariance tracking algorithm and the choice of variable selection scheme is too complex to be dealt with analytically. We hence capitalise on the strength of simulations to explore this problem, taking the opportunity to tackle the difficult task of simulating dynamic correlation structures. © 2008 IEEE.

Fine scale structures from deformation of aluminium containing small alumina particles

Microstructures and mechanical properties have been studied in aluminium containing a fine dispersion of alumina particles, deformed by cold-rolling to strains between 1.4 and 3.5. The microstructure was characterised by TEM. The deformation structures evolved very rapidly, forming a nanostructured material, with fine subgrains about 0.2 μm in diameter and a fraction of high-angle boundaries which was already high at a strain of 1.4, but continued to increase with rolling strain. The yield stress and ductility of the rolled materials were measured in tension, and properties were similar for all materials. Yield stress measurements were correlated with estimates made using microstructural models. The role of small particles in forming and stabilising the deformation structure is discussed. This nanostructured cold-deformed alloy has mechanical properties which are usefully enhanced at comparatively low cost. This gives it, and similar particle-strengthened alloys, good potential for commercial exploitation. © 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

Independent component analysis of microarray data in the study of endometrial cancer.

Gene microarray technology is highly effective in screening for differential gene expression and has hence become a popular tool in the molecular investigation of cancer. When applied to tumours, molecular characteristics may be correlated with clinical features such as response to chemotherapy. Exploitation of the huge amount of data generated by microarrays is difficult, however, and constitutes a major challenge in the advancement of this methodology. Independent component analysis (ICA), a modern statistical method, allows us to better understand data in such complex and noisy measurement environments. The technique has the potential to significantly increase the quality of the resulting data and improve the biological validity of subsequent analysis. We performed microarray experiments on 31 postmenopausal endometrial biopsies, comprising 11 benign and 20 malignant samples. We compared ICA to the established methods of principal component analysis (PCA), Cyber-T, and SAM. We show that ICA generated patterns that clearly characterized the malignant samples studied, in contrast to PCA. Moreover, ICA improved the biological validity of the genes identified as differentially expressed in endometrial carcinoma, compared to those found by Cyber-T and SAM. In particular, several genes involved in lipid metabolism that are differentially expressed in endometrial carcinoma were only found using this method. This report highlights the potential of ICA in the analysis of microarray data.

The question of ethical decision in marketing and ethics

Resumen: Mientras que el marketing está asociado con prácticas negativas que involucran la explotación y la deshonestidad, Anton Jamnik afirma la necesidad de crear una teoría ética para éste. El artículo intenta brindar, por un lado, un breve bosquejo de las principales corrientes de la literatura de la ética del marketing y, por otro, participar de su desarrollo. El autor analiza los desafíos éticos que sur girán en el futuro, provenientes de tres fuentes distintas: las innovaciones tecnológicas, la influencia de la competencia global y la expansión de las actividades de mercado en áreas no tradicionales. Esto requerirá el desarrollo de una ética normativa realista. Para concluir, explica que la ética del marketing debería analizar hasta qué punto ha sido exitosa a la hora de resolver los desafíos éticos del mundo actual.

El aprovisionamiento de leña en las ciudades de la baja edad media hispánica

Resumen: Desde hace algunos años los estudios sobre el abastecimiento en la España Medieval han ido aumentando considerablemente. En nuestro país, la Dra. Carlé ha sido una de las pioneras en estos tópicos –como en tantos otros–, abriendo las puertas a esta temática trabajada posteriormente por muchos investigadores. En esta oportunidad, el objetivo de este trabajo es mostrar cómo se percibe este “delicado equilibrio” existente entre explotación/conservación en algunas ordenanzas municipales de los siglos XV y XVI, referidas al consumo y comercialización de la “lenna”.

Estrategias de gestión y producción escénica en el teatro independiente argentino de 2001 a 2011

Resumen: Este ensayo establece una territorialización de los lenguajes teatrales alternativos como zona específica de la cultura urbana, y los historiza en la tradición de la escena independiente argentina. Analiza el contexto específico de la crisis financiera que eclosionó en 2001 y la producción más reciente, dando cuenta de un periodo tan conflictivo en lo económico como prolífico en lo teatral. Se describen las actividades de gestión y producción escénicas, que incluyen la búsqueda de espacios, subsidios y respaldo institucional, y la implementación de estrategias de difusión y explotación. Estas labores específicas son desarrolladas de manera particular por numerosos teatristas argentinos de entre 30 y 40 años, ya legitimados, incluso a nivel internacional. Estos dramaturgos-actores-directores co-construyen representaciones sociales compartidas, y manifiestan diferentes modalidades estratégicas asociativas, tales como la rotación de roles y el trabajo en colaboración.

Second-best tax policy in a growing economy with externalities

This paper investigates the exploitation of environmental resources in a growing economy within a second-best scal policy framework. Agents derive utility from two types of consumption goods one which relies on an environmental input and one which does not as well as from leisure and from environmental amenity values. Property rights for the environmental resource are potentially incomplete. We connect second best policy to essential components of utility by considering the elasticity of substitution among each of the four utility arguments. The results illustrate potentially important relationships between environmental amentity values and leisure. When amenity values are complementary with leisure, for instance when environmental amenities are used for recreation, taxes on extractive goods generally increase over time. On the other hand, optimal taxes on extractive goods generally decrease over time when leisure and environmental amenity values are substitutes. Unders some parameterizations, complex dynamics leading to nonmonotonic time paths for the state variables can emerge.

The Evaluation of Fisheries Management: A Dynamic Stochastic Approach

In this article, we analyze how to evaluate fishery resource management under “ecological uncertainty”. In this context, an efficient policy consists of applying a different exploitation rule depending on the state of the resource and we could say that the stock is always in transition, jumping from one steady state to another. First, we propose a method for calibrating the growth path of the resource such that observed dynamics of resource and captures are matched. Second, we apply the calibration procedure proposed in two different fishing grounds: the European Anchovy (Division VIII) and the Southern Stock of Hake. Our results show that the role played by uncertainty is essential for the conclusions. For European Anchovy fishery (Division VIII) we find, in contrast with Del Valle et al. (2001), that this is not an overexploited fishing ground. However, we show that the Southern Stock of Hake is in a dangerous situation. In both cases our results are in accordance with ICES advice.

Mortality estimates of the four major Cichlid fishes of Umuoseriche Lake, Imo State, Nigeria

The mortality of the four major cichlid fishes of Urnuoseriche Lake is the subject of this paper. Mortality I as estimated by five techniques, vary amongst the cichlid fishes, viz, Tilapia carbrae, Tilapia mariac, Tilapia zilli cend (hrornoditilapfa guntheri. The highest mortality rate was recorded for T mariac where the total mortality (Z) was 2.06; and natural mortality (M) was 1.8949. This species was also the most highly exploited species of fish with an exploitation ratio of0.566 (56.6%) and exploitation rate of 0.494. The least exploited cichlid fish is (. gun/hen where an exploitation ratio of 0.43209%) and exploitation rate of 0.2225 was recorded. In C'. guntheni, total mortality was 0.726 and natural mortality was 0.413 1. In T zilli, total mortality was 1.0547 wile exploitation ratio was 0.3674 (3 6.74%) and an exploitation rate was 0.2394. In T cahrae. total mortality was 1.8662: exploitation ratio was 0.4786 with an exploitation rate of 0.4045. (7 page document)

Technology Outlook as a tool for the management of innovation

[EN] The purpose of this paper is to present a theoretical overview of innovation management and the tools that can aid in this endeavour. The paper adopts a user-oriented description, aiming at making SMEs familiar with the possibilities opened by innovation management tools in general and technology outlook in particular.

Astarloaren Discursos filosóficos: iturrak eta axiomak

Astarloa's Discursos filosóficos is the most extensive and detailed apology of the Basque language as the first language of mankind. The text was finished in 1805 but the first edition was published in 1883. In this paper I attempt to sketch the main linguistic and philosophic ideas that could have an influence in Astarloa's thought. Then I deal with Astarloa's characterization of the first language, and the three principles he used to verify that Basque was that first language of human beings.