Metathesis as a versatile tool in oleochemistry

Olefin metathesis, awarded with the Nobel Prize in Chemistry 2005 for Chauvin, Grubbs and Schrock, has emerged as a powerful tool for organic as well as polymer chemistry. In oleochemistry, this reaction is well known and has been applied for many decades. Examples include the functionalization of the double bonds of different oleochemicals or the (direct) polymerization of plant oils via metathesis. More recent developments, particularly the development of better and more robust catalysts, allow for highly efficient cross‐metathesis reactions opening new possibilities for the direct introduction of chemical functionalities. Within this contribution, the development of metathesis in oleochemistry will be discussed, covering self‐metathesis as well as more recent developments in the field of cross‐metathesis that lead to desired platform chemicals.     

Ring‐opening polymerization of D,L‐lactide by rare earth 2,6‐dimethylaryloxide

Ring‐opening polymerization of D,L ‐lactide (LA) has been successfully carried out by using rare earth 2,6‐dimethylaryloxide (Ln(ODMP)₃) as single component catalyst or initiator for the first time. The effects of different rare earth elements, solvents, monomers and catalyst concentration as well as polymerization temperature and time on the polymerization were investigated. The results show that La(ODMP)₃ exhibits higher activity to prepare poly(D,L ‐lactide) (PLA) with a viscosity molecular weight of 4.5 × 10⁴ g mol^?1 and the conversion of 97 % at 100 °C in 45 min. The catalytic activity of Ln(ODMP)₃ has following sequence: La > Nd > Sm > Gd > Er > Y. A kinetic study has indicated that the polymerization is first order with respect to both monomer and catalyst concentration. The apparent activation energy of the polymerization of LA with La(ODMP)₃ is 69.6 kJ mol^?1. The analyses of polymer ends indicate that the LA polymerization proceeds according to ‘coordination–insertion’ mechanism with selective cleavage of the acyl–oxygen bond of the monomer. Copyright © 2004 Society of Chemical Industry     

大窝山隧道进口围岩快速掘进施工组织与管理

结合工程概况及工程特点,从机械设备配置、劳动力组织、现场管理等方面介绍了大窝山隧道进口Ⅱ级,Ⅲ级围岩段的快速掘进施工组织与管理措施,为类似隧道的快速掘进施工组织与管理提拱了相关经验.     

Performance evaluation of a water/silicone oil two‐phase partitioning bioreactor using Rhodococcus erythropolis T902.1 to remove volatile organic compounds from gaseous effluents

BACKGROUND: In the framework of biological processes used for waste gas treatment, the impact of the inoculum size on the start‐up performance needs to be better evaluated. Moreover, only a few studies have investigated the behaviour of elimination capacity and biomass viability in a two‐phase partitioning bioreactor (TPPB) used for waste gas treatment. Lastly, the impact of ethanol as a co‐substrate remains misunderstood. RESULTS: Firstly, no benefit of inoculation with a high cellular density (>1.5 g L^?1) was observed in terms of start‐up performance. Secondly, the TPPB was monitored for 38 days to characterise its behaviour under several operational conditions. The removal efficiency remained above 63% for an inlet concentration of 7 g isopropylbenzene (IPB) m^?3 and at some time points reached 92% during an intermittent loading phase (10 h day^?1), corresponding to a mean elimination capacity of 4 × 10^?3 g L^?1 min^?1 (240 g m^?3 h^?1) for a mean IPB inlet load of 6.19 × 10^?3 g L^?1 min^?1 (390 g m^?3 h^?1). Under continuous IPB loading, the performance of the TPPB declined, but the period of biomass acclimatisation to this operational condition was shorter than 5 days. The biomass grew to approximately 10 g L^?1 but the cellular viability changed greatly during the experiment, suggesting an endorespiration phenomenon in the bioreactor. It was also shown that simultaneous degradation of IPB and ethanol occurred, suggesting that ethanol improves the biodegradation process without causing oxygen depletion. CONCLUSION: A water/silicone oil TPPB with ethanol as co‐substrate allowed the removal of a high inlet load of IPB during an experiment lasting 38 days. Copyright © 2008 Society of Chemical Industry     

Innovation in construction: a sociology of technology approach

An alternative approach to understanding innovation is made using two intersecting ideas. The first is that successful innovation requires consideration of the social and organizational contexts in which it is located. The complex context of construction work is characterized by inter-organizational collaboration, a project-based approach and power distributed amongst collaborating organizations. The second is that innovations can be divided into two modes: 'bounded', where the implications of innovation are restricted within a single, coherent sphere of influence, and 'unbounded', where the effects of implementation spill over beyond this. Bounded innovations are adequately explained within the construction literature. However, less discussed are unbounded innovations, where many firms' collaboration is required for successful implementation, even though many innovations can be considered unbounded within construction's inter-organizational context. It is argued that unbounded innovations require an approach to understand and facilitate the interactions both within a range of actors and between the actors and technological artefacts. The insights from a sociology of technology approach can be applied to the multiplicity of negotiations and alignments that constitute the implementation of unbounded innovation. The utility of concepts from the sociology of technology, including 'system building' and 'heterogeneous engineering', is demonstrated by applying them to an empirical study of an unbounded innovation on a major construction project (the new terminal at Heathrow Airport, London, UK). This study suggests that 'system building' contains outcomes that are not only transformations of practices, processes and systems, but also the potential transformation of technologies themselves.     

The Minimum PAPR Code for OFDM Systems

In this letter, a block code that minimizes the peak‐to‐average power ratio (PAPR) of orthogonal frequency division multiplexing (OFDM) signals is proposed. It is shown that peak envelope power is invariant to cyclic shift and codeword inversion. The systematic encoding rule for the proposed code is composed of searching for a seed codeword, shifting the register elements, and determining codeword inversion. This eliminates the look‐up table for one‐to‐one correspondence between the source and the coded data. Computer simulation confirms that OFDM systems with the proposed code always have the minimum PAPR.     

Inverted Solution Processable OLEDs Using a Metal Oxide as an Electron Injection Contact.

A new type of bottom‐emission electroluminescent device is described in which a metal oxide is used as the electron‐injecting contact. The preparation of such a device is simple. It consists of the deposition of a thin layer of a metal oxide on top of an indium tin oxide covered glass substrate, followed by the solution processing of the light‐emitting layer and subsequently the deposition of a high‐workfunction (air‐stable) metal anode. This architecture allows for a low‐cost electroluminescent device because no rigorous encapsulation is required. Electroluminescence with a high brightness reaching 5700 cd m^–2 is observed at voltages as low as 8 V, demonstrating the potential of this new approach to organic light‐emitting diode (OLED) devices. Unfortunately the device efficiency is rather low because of the high current density flowing through the device. We show that the device only operates after the insertion of an additional hole‐injection layer in between the light‐emitting polymer (LEP) and the metal anode. A simple model that explains the experimental results and provides avenues for further optimization of these devices is described. It is based on the idea that the barrier for electron injection is lowered by the formation of a space–charge field over the metal‐oxide–LEP interface due to the build up of holes in the LEP layer close to this interface.     

Optimal and self‐tuning fusion Kalman filters for discrete‐time stochastic singular systems

Based on the optimal fusion estimation algorithm weighted by scalars in the linear minimum variance sense, a distributed optimal fusion Kalman filter weighted by scalars is presented for discrete‐time stochastic singular systems with multiple sensors and correlated noises. A cross‐covariance matrix of filtering errors between any two sensors is derived. When the noise statistical information is unknown, a distributed identification approach is presented based on correlation functions and the weighted average method. Further, a distributed self‐tuning fusion filter is given, which includes two stage fusions where the first‐stage fusion is used to identify the noise covariance and the second‐stage fusion is used to obtain the fusion state filter. A simulation verifies the effectiveness of the proposed algorithm. Copyright © 2008 John Wiley & Sons, Ltd.     

Impact of the addition of an enzyme pool on an activated sludge system treating dairy wastewater under fat shock loads

BACKGROUND: The application of lipase‐rich enzyme pools (such as the crude solid enzymatic preparation (SEP) obtained from Penicillium restrictum solid‐state fermentation of agro‐industrial wastes) to activated sludge systems may be an effective strategy for preventing various operational problems. The continuous addition of SEP to the treatment system can become cost‐prohibitive when in situ production and/or storage are factored in. The application of SEP to high‐fat wastewater treatment would only be justified as an emergency measure, such as a sudden increase in the fat content of the bioreactor influent. Therefore, the primary objective of this work was to investigate the efficiency of a crude SEP during fat shock loads, simulated through the periodic addition of dairy industry waste containing high fat concentrations to the feed stock of an activated sludge system, operated in continuous mode. RESULTS: The test bioreactor exhibited a higher average chemical oxygen demand (COD) removal efficiency than the control bioreactor (83% for control and 90% for test) and the fat accumulation in the biological flocs of the test bioreactor was 3.2 times lower than that in the control bioreactor. Turbidity was also lower in the effluent of the test bioreactor (123 and 66 FTU in control and test, respectively) and it had a shorter recovery time between shock loads, especially when the interval between loads was shorter than one month (biweekly and weekly shock loads). CONCLUSION: The addition of SEP during fat overloads in the reactor feed maintained efficient COD removal in the test bioreactor for 270 days without any operational problems. Copyright © 2008 Society of Chemical Industry     

Sensitometric characteristics of an all‐solid‐state photoelectrochromic pixel for an electrochromic light‐addressable display

Abstract— An all solid‐state photoelectrochromic element (PECE) was developed on the basis of electrochromic layers of WO₃ and polyaniline with a layer of polymer electrolyte placed on a base of polyamidosulfoacid, in which a thin‐film CdS_xSe_1?x photoresistor was used as an electronic key. The dependence of the sensitometric characteristics of the PECE on the applied voltage was studied.