The synthesis and X-ray crystal structure of 6-bromo-2,4,4-trimethyl-cyclohex-2-enone

Regiospecific bromination of 2,4,4-trimethyl-cyclohex-2-enone was achieved and the X-ray crystal structure of 6-bromo-2,4,4-trimethyl-cyclohex-2-enone is presented.

The synthesis and X-ray crystal structure of 9-carboxyhexahydro-7-methoxy-4a,7-ethano-benzopyran-5-en-1-one

9-Carboxyhexahydro-7-methoxy-4a,7-ethano-benzopyran-5-en-1-one (1) was prepared and examined by X-ray crystallography to probe its potential as a new peptide scaffold/template. The crystal structure of the anhydride precursor 7-(2-acetoxyethyl)-4-methoxy-3a,4,7,7a-tetrahydro-4,7-ethanoisobenzofuran-1,3-dione (6) is also reported.

Piezoresistive sensors for force mapping of hip-prostheses

The success of artificial prosthetic replacements depends on the fixation of the artificial prosthetic component after being implanted in the thighbone. The materials for fixation are subject to mechanical stresses, which originate permanent deformations, incipient cracks and even fatigue fractures. This work shows the possibility of monitoring the mechanical stress over time in prosthesis. In this way, highly sensitive silicon thin-film piezoresistive sensors were developed attached to prosthesis and their results compared with commercial strain gauge sensors. Mechanical stress-strain experiments were performed in compressive mode, during 10,000 cycles. Experimental data was acquired at mechanical vibration frequencies of 0.5 Hz, 1 Hz and 5 Hz, and sent to a computer by means of a wireless link. The results show that there is a decrease in sensitivity of the thin-film silicon piezoresistive sensors when they are attached to the prosthesis, but this decrease does not compromise its monitoring performance. The sensitivity, compared to that of commercial strain gauges, is much larger due to their higher gauge factors (-23.5), when compared to the GFs of commercial sensors (2).

Component identification through program slicing

This paper reports on the development of specific slicing techniques for functional programs and their use for the identification of possible coherent components from monolithic code. An associated tool is also introduced. This piece of research is part of a broader project on program understanding and re-engineering of legacy code supported by formal methods

SHACC: a functional prototyper for a component calculus

Over the last decade component-based software development arose as a promising paradigm to deal with the ever increasing complexity in software design, evolution and reuse. SHACC is a prototyping tool for component-based systems in which components are modelled coinductively as generalized Mealy machines. The prototype is built as a HASKELL library endowed with a graphical user interface developed in Swing

On the specification of a component repository

The lack of a commonly accepted de nition of a software component, the proliferation of competing `standards' and component frameworks, is here to stay, raising the fundamental question in component-based development of how to cope in practice with heterogeneity. This paper reports on the design of a Component Repository aimed to give at least a partial answer to the above question. The repository was fully speci ed in Vdm and a working prototype is currently being used in an industrial environment

IDEA MANAGEMENT SYSTEM - AN ESSENTIAL COMPONENT IN THE CONTINUOUS IMPROVEMENT OF QUALITY AND INNOVATION

It is known the power of ideas is tremendous. But there are employees in many companies who have good ideas but not put them into practice. On the other hand, there are many others who have good ideas and are encouraged to contribute their ideas for innovation in the company. This study attempts to identify factors that contribute to success in managing ideas and consequent business innovation. The method used was the case study applied to two companies. During the investigation, factors considered essential for the success of an idea management program were identified, of which we highlight, among others, evidences the results, involvement of the top management, establishment of goals and objectives; recognition; dissemination of good results. Companies with these implemented systems, capture the best ideas from their collaborators and apply them internally. This study intends to contribute to business innovation in enterprises through creation and idea management, mainly through collecting the best ideas of their own employees. The results of this study can be used to help improving deployed suggestions systems, as well as, all managers who wish to implement suggestions systems/ideas management systems.

n-Hexane hydroisomerisation over bifunctional Pt/MCM-22 catalysts. Influence of the mode of Pt introduction

Three different methods were used to introduce 1.0 wt.% of Pt in bifunctional Pt/MCM-22 zeolite catalysts: ion exchange with Pt(NH3)(4)(2+), incipient wetness impregnation with PtCl6H2 and mechanical mixture with Pt/Al2O3. The Pt dispersion was estimated by transmission electron microscopy and the hydrogenating activity with toluene hydrogenation at 110 degrees C. From these experiments, it can be concluded that with the ion exchanged sample, platinum was located within the inner micropores and on the outer surface, whereas with the impregnated one, platinum was essentially on the outer surface under the form of large particles. With all the samples there is a fast initial decrease in the activity for n-hexane hydroisomerisation at 250 degrees C. With exchanged and impregnated samples, this decrease is followed by a plateau, the activity value being then higher with impregnated sample. For the sample prepared by mechanical mixture a continuous decrease in activity can be observed. All these differences can be related with the distinct locations of Pt.

Synthesis, structure, and optical properties of an alternating calix[4]arene-based meta-linked phenylene ethynylene copolymer

Novel alternating copolymers comprising biscalix[4]arene-p-phenylene ethynylene and m-phenylene ethynylene units (CALIX-m-PPE) were synthesized using the Sonogashira-Hagihara cross-coupling polymerization. Good isolated yields (60-80%) were achieved for the polymers that show M-n ranging from 1.4 x 10(4) to 5.1 x 10(4) gmol(-1) (gel permeation chromatography analysis), depending on specific polymerization conditions. The structural analysis of CALIX-m-PPE was performed by H-1, C-13, C-13-H-1 heteronuclear single quantum correlation (HSQC), C-13-H-1 heteronuclear multiple bond correlation (HMBC), correlation spectroscopy (COSY), and nuclear overhauser effect spectroscopy (NOESY) in addition to Fourier transform-Infrared spectroscopy and microanalysis allowing its full characterization. Depending on the reaction setup, variable amounts (16-45%) of diyne units were found in polymers although their photophysical properties are essentially the same. It is demonstrated that CALIX-m-PPE does not form ground-or excited-state interchain interactions owing to the highly crowded environment of the main-chain imparted by both calix[4]arene side units which behave as insulators inhibiting main-chain pi-pi staking. It was also found that the luminescent properties of CALIX-m-PPE are markedly different from those of an all-p-linked phenylene ethynylene copolymer (CALIX-p-PPE) previously reported. The unexpected appearance of a low-energy emission band at 426 nm, in addition to the locally excited-state emission (365 nm), together with a quite low fluorescence quantum yield (Phi = 0.02) and a double-exponential decay dynamics led to the formulation of an intramolecular exciplex as the new emissive species.

Stability Condition Based Sliding Mode Modulators for Multilevel Power Converters

Sliding mode controllers for power converters usually employ hysteresis comparators to directly generate the power semiconductors switching states. This paper presents a new sliding mode modulator based on the direct implementation of the sliding mode stability condition, which for multilevel power converters shows advantages, as branch equalized switching frequencies and less distortion on the ac currents when operating near the rated converter power. The new sliding mode multilevel modulator is used to control a three-phase multilevel converter, operated as a reactive power compensator (STATCOM), implementing the stability condition in a digital signal processing system. The performance of this new sliding mode modulator is compared with a multilevel modulator based on hysteresis comparators. Simulation and experimental results are presented in order to highlight the system operation and control robustness.

Templated synthesis of carbon materials mediated by porous clay heterostructures

Mesoporous carbon materials were prepared through template method approach using porous clay heterostructures (PCHs) as matrix and furfuryl alcohol as carbon precursor. Three PCHs prepared using amines with 8, 10 and 12 carbon atoms were used. The effect of several impregnation-polymerization cycles of the carbon precursor, the carbonization temperature and the need of a previous surface alumination were evaluated. The presence of two porosity domains was identified in all the carbon materials. These two domains comprise pores resulting from the carbonization of the polymer film formed in the inner structure of the PCH (domain I) and larger pores created by the clay particles aggregation (domain II). The predominance of the porosity associated to domain I or II can be achieved by choosing a specific amine to prepare the PCH matrix. Carbonization at 700 C led to the highest development of pores of domain I. In general, the second impregnation-polymerization cycle of furfuryl alcohol resulted in a small decrease of both types of porosity domains. Furthermore the previous acidification of the surface to create acidic sites proved to be unnecessary. The results showed the potential of PCHs as matrices to tailor the textural properties of carbons prepared by template mediated synthesis.

Low Complexity Intra Mode Selection for Efficient Distributed Video Coding

Motion compensated frame interpolation (MCFI) is one of the most efficient solutions to generate side information (SI) in the context of distributed video coding. However, it creates SI with rather significant motion compensated errors for some frame regions while rather small for some other regions depending on the video content. In this paper, a low complexity Infra mode selection algorithm is proposed to select the most 'critical' blocks in the WZ frame and help the decoder with some reliable data for those blocks. For each block, the novel coding mode selection algorithm estimates the encoding rate for the Intra based and WZ coding modes and determines the best coding mode while maintaining a low encoder complexity. The proposed solution is evaluated in terms of rate-distortion performance with improvements up to 1.2 dB regarding a WZ coding mode only solution.

Molybdenum Complexes Bearing the Tris(1-pyrazolyl)methanesulfonate Ligand: Synthesis, Characterization and Electrochemical Behaviour

The tris(1-pyrazolyl)methanesulfonate lithium salt Li(Tpms) [Tpms = SO3C(pz)(3)-] reacts with [Mo(CO)(6)] in NCMe heated at reflux to yield Li[Mo(Tpms)(CO)(3)] (1), which, upon crystallization from thf, forms the coordination polymer [Mo(Tpms)(CO)(2)(mu-CO)Li(thf)(2)](n) (2). Reaction of 1 with I-2, HBF4 or AgBF4 yields [Mo(Tpms)I(CO)(3)] (3), (Mo(Tpms)-H(CO)(3)] (5) or (Mo(Tpms)O-2](2)(mu-O) (7), respectively. The high-oxidation-state dinuclear complexes [{Mo(Tpms)O(mu-O)}(2)] (4) and [{Mo(tpms)OCl)(2)](mu-O) (6) are formed upon exposure to air of solutions of 3 and 5, respectively. Compounds 1-7, which appear to be the first tris(pyrazolyl)methanesulfonate complexes of molybdenum to be reported, were characterized by IR, H-1 and C-13 NMR spectroscopy, ESI-MS, elemental analysis, cyclic voltammetry and, in the cases of Li(Tpms) and compounds 2, 4.2CH(3)CN, 6.6CHCl(3) and 7, by X-ray diffraction analyses. Li(Tpms) forms a 1D polymeric structure (i.e., [Li(tpms)](n)} with Tpms as a tetradentate N2O2 chelating ligand that bridges two Li cations with distorted tetrahedral coordination. Compound 2 is a 1D coordination polymer in which Tpms acts as a bridging tetradentate N3O ligand and each Li(thf)(2)(+) moiety is coordinated by one bridging CO ligand and by the sulfonyl group of a contiguous monomeric unit. In 4, 6 and 7, the Tpms ligand is a tridentate chelator either in the NNO (in 4) or in the NNN (in 6 and 7) fashion. Complexes 1, 3 and 5 exhibit, by cyclic voltammetry, a single-electron oxidation at oxidation potential values that indicate that the Tpms ligand has an electron-donor character weaker than that of cyclopentadienyl.

A dramatic effect of double bond configuration in N-oxy-3-aza Cope rearrangements: a simple synthesis of functionalised allenes

The first examples of low temperature N-oxy-3-aza Cope rearrangements, leading to functionalised allenes are described, where the Z-configuration of the enaminic double bond in the rearranging system proves critical.

Asymmetric synthesis of N-aryl aziridines

The reactions of a variety of N-arylhydroxamates as nitrogen transfer reagents to acryloyl derivatives of (−)-8-phenylmenthol, (−)-quinine and (−)-Oppolzer’s sultam acting as Michael acceptors was studied. Poor to modest diastereoselection was observed in the formation of aziridines. The absolute structure of one of the pure diastereomers secured from Oppolzer’s auxiliary was established by X-ray crystallography and hence the absolute configuration of the derived methyl-N-phenylaziridine-2-carboxylate could be assigned. Whilst only poor facial selectivity was observed for chiral hydroxamic acid prepared from dehydroabietic acid, moderate to good enantioselection of aziridines could be achieved with the chiral quaternary salts based on cinchona alkaloids, especially with that of cinchonine. A model is presented to explain the origin of enantioselection and a mechanism is proposed for the aziridination reaction.