Molecular Determinants of Carbocation Cyclisation in Bacterial Monoterpene Synthases

Monoterpene synthases are often promiscuous enzymes, yielding product mixtures rather than pure compounds due to the nature of the branched reaction mechanism involving reactive carbocations. Two previously identified bacterial monoterpene synthases, a linalool synthase (bLinS) and a cineole synthase (bCinS), produce nearly pure linalool and cineole from geranyl diphosphate, respectively. We used a combined experimental and computational approach to identify critical residues involved in bacterial monoterpenoid synthesis. Phe77 is essential for bCinS activity, guiding the linear carbocation intermediate towards the formation of the cyclic α-terpinyl intermediate; removal of the aromatic ring results in variants that produce acyclic products only. Computational chemistry confirmed the importance of Phe77 in carbocation stabilisation. Phe74, Phe78 and Phe179 are involved in maintaining the active site shape in bCinS without a specific role for the aromatic ring. Phe295 in bLinS, and the equivalent Ala301 in bCinS, are essential for linalool and cineole formation, respectively. Where Phe295 places steric constraints on the carbocation intermediates, Ala301 is essential for bCinS initial cyclisation and activity. Our multidisciplinary approach gives unique insights into how carefully placed amino acid residues in the active site can direct carbocations down specific paths, by placing steric constraints or offering stabilisation via cation-π interactions.     

Optimization of E. coli tip-sonication for high-yield cell-free extract using finite element modeling

Optimal tip sonication settings, namely tip position, input power, and pulse durations, are necessary for temperature sensitive procedures like preparation of viable cell extract. In this paper, the optimum tip immersion depth (20–30% height below the liquid surface) is estimated which ensures maximum mixing thereby enhancing thermal dissipation of local cavitation hotspots. A finite element (FE) heat transfer model is presented, validated experimentally with (R² > 97%) and used to observe the effect of temperature rise on cell extract performance of Escherichia coli BL21 DE3 star strain and estimate the temperature threshold. Relative yields in the top 10% are observed for solution temperatures maintained below 32°C; this reduces below 50% relative yield at temperatures above 47°C. A generalized workflow for direct simulation using the CONSOL code as well as master plots for estimation of sonication parameters (power input and pulse settings) is also presented.     

Thermal Response of Steel–Steel Composite Metal Foams under Small-Scale Torch-Fire Conditions

Steel–steel composite metal foam (S–S CMF) is a novel metal matrix composite material characterized by its high strength-to-weight ratio and unique mechanical and thermal properties. It is made up of hollow stainless-steel spheres, embedded in stainless steel matrix, with 65–70% air in the structure making it effective as an insulating material. S–S CMF is being explored for use in tank cars carrying hazardous materials (HAZMATs) as a potential partial replacement for conventional carbon steel and thermal insulating material currently being used. In this study, S–S CMF material is numerically and experimentally evaluated for its thermal protection performance. Experimental studies are conducted in scaled-down jet fire condition while numerical studies are conducted using fire dynamics simulator (FDS). Based on experimental and modeling results, as well as uncertainty studies, 13–15 mm thick S–S CMF ranging in density of about 2.5 g cc⁻¹ tested as novel structural/insulating material meets the acceptance criterion for small-scale simulated torch-fire testing. Further success is anticipated in future full-scale evaluation of 122 × 122 cm samples. The outstanding fire resistance and thermal protection of S–S CMF is attributed to the substantial volume of air trapped within the material, which correlates to its total density.     

Current status and future trends for disposable technology in the biopharmaceutical industry

Single use technology (SUT) is in widespread use throughout the biopharmaceutical industry where it is replacing traditional stainless steel plant particularly for the manufacture of small volume, high value products. The key drivers for SUT uptake include reduction of regulatory risk, lower capital and energy costs and increased facility flexibility. Disposable technology is now well established for cell culture, liquid handling and storage but its application to some downstream operations is proving more intractable. Single‐use chromatography resins are generally uneconomic at process scale and there are limitations on large‐scale tangential flow filtration capacities. The development of disposable sensor technology is lagging behind that of bioreactors and capacities for microbial culture are presently limited to 2000 litres. Concerns regarding compatibility of equipment from different suppliers and extractable and leachable testing are being addressed but continue to influence uptake of SUT by traditional manufacturers. Complete ‘plug and play’ disposable process trains, however, are becoming increasingly available and are being embraced by Contract Manufacturing Organisations (CMOs) with multiproduct facilities. © 2013 Society of Chemical Industry     

An approach to setting ecological flow thresholds for southern English chalk streams

This paper presents a study of 10 English chalk streams in the River Thames Basin historically affected by abstraction of groundwater. Using macroinvertebrates, macrophytes and river discharge records from across 76 monitoring sites, and spanning the period 1992–2009 we assess how the communities change over time. River discharge is seen to be the most influential variable in biological community composition, and is used to calculate the annual average river discharge (in m³/s) needed to sustain different biological assemblages at each study site, from the lowest to the highest expression of fluvial aquatic community development. This represents a bottom‐up or site‐specific approach to the determination of ecological flow thresholds, from which more empirical trends may be inferred at regional level. The approach also provides a useful understanding of the timescales involved in the recovery of communities from drought.     

2012伦敦奥林匹克公园的生态种植设计

介绍了詹姆斯·希契莫夫(James Hitehmough)和奈杰尔·邓内特(Nigel Dunnett)教授为2012年伦敦奥林匹克公园设计和营造草本植物群落景观的相关工作.伦敦奥林匹克公园可能是奥运会发展至今最具可持续发展观的,这一理念在250hm2的绿地景观中得到了充分展示.场地种植设计的亮点,是营建生态结构合理的植物群落以最大尺度的实现稳定可持续性.形态和季相色彩丰富的绿地景观不仅为奥运会期间的游人服务,之后大部分的景观会得以保留,进而成为伦敦东部的一个新的地区公园.描述和讨论了公园和自然式的种植设计在当前追求更加持续稳定的城市环境设计中的实践和理论哲学地位.     

Absolute linearity measurements on HgCdTe detectors in the infrared region

The nonlinearity characteristics of photoconductive and photovoltaic HgCdTe detectors were experimentally investigated in the infrared wavelength region by use of the National Physical Laboratory detector linearity measurement facility. The nonlinearity of photoconductive HgCdTe detectors was shown to be a function of irradiance rather than the total radiant power incident on the detector. Photoconductive HgCdTe detectors supplied by different vendors were shown to have similar linearity characteristics for wavelengths around 10 microm. However, the nonlinearity of response of a photovoltaic HgCdTe detector was shown to be significantly lower than the corresponding value for photoconductive HgCdTe detectors at the same wavelength.     

Transient electroluminescence determination of carrier mobility and charge trapping effects in heavily doped phosphorescent organic light-emitting diodes

Transient electroluminescence (EL) was used to measure the delay between the excitation pulse and onset of emission in OLEDs based on phosphorescent bis[3,5-bis(2-pyridyl)-1,2,4-triazolato] platinum(ΙΙ) doped into 4,4′-bis(carbazol-9-yl) triphenylamine (CBP), from which an electron mobility of 3.2 × 10⁻⁶ cm²/V s was approximated. Delayed recombination was observed after the drive pulse had been removed and based on its dependence on frequency and duty cycle, ascribed to trapping and de-trapping processes associated with disorder-induced carrier localization at the interface between the emissive layer and electron blocker. The data suggests that the exciton recombination zone is at, or close to the interface between the emissive layer and electron blocker. Despite the charge trapping effects, a peak power efficiency of 24 lm/W and peak external quantum efficiency of 10.64% were obtained. Mechanisms for the electroluminescence and delayed recombination are proposed.