Amino Acid Residues Controlling Domain Interaction and Interdomain Electron Transfer in Cellobiose Dehydrogenase

The function of cellobiose dehydrogenase (CDH) in biosensors, biofuel cells, and as a physiological redox partner of lytic polysaccharide monooxygenase (LPMO) is based on its role as an electron donor. Before donating electrons to LPMO or electrodes, an interdomain electron transfer from the catalytic FAD-containing dehydrogenase domain to the electron shuttling cytochrome domain of CDH is required. This study investigates the role of two crucial amino acids located at the dehydrogenase domain on domain interaction and interdomain electron transfer by structure-based engineering. The electron transfer kinetics of wild-type Myriococcum thermophilum CDH and its variants M309A, R698S, and M309A/R698S were analyzed by stopped-flow spectrophotometry and structural effects were studied by small-angle X-ray scattering. The data show that R698 is essential to pull the cytochrome domain close to the dehydrogenase domain and orient the heme propionate group towards the FAD, while M309 is an integral part of the electron transfer pathway – its mutation reducing the interdomain electron transfer 10-fold. Structural models and molecular dynamics simulations pinpoint the action of these two residues on the domain interaction and interdomain electron transfer.     

Comparison of two different types of railway ballast in compression and direct shear tests: experimental results and DEM model validation

Railway ballast is an angular and coarse material, which demands careful DEM modelling and validation. Particle shape is often modelled in high accuracy, thus leading to computational expensive DEM models. Whether this effort will increase the DEM model’s overall prediction quality will also vitally depend on the used contact law and the validation process. In general, a DEM model validated using different types of principal experiments can be considered more trustworthy in simulating other load cases. Here, two types of railway ballast are compared and DEM model validation is conducted. Calcite and Kieselkalk are investigated under compression and direct shear test. All experimental data will be made openly accessible to promote further research on this topic. In the experiments, the behaviour of Calcite and Kieselkalk is surprisingly similar in the direct shear test, while clear differences can be seen in the stiffnesses in the compression test. In DEM modelling, simple particle shapes are combined with the Conical Damage Model contact law. For each type of ballast, one set of parameters is found, such that simulation and experimental results are in good accordance. A comparison with the simplified Hertz-Mindlin contact law shows several drawbacks of this model. First, the model cannot be calibrated to meet both compression and shear test results. Second, the similar behaviour in shear testing but differences in compression cannot be reproduced using the Hertz-Mindlin model. For these reasons, the CDM model is considered the better choice for the simulation of railway ballast, if simple particle shapes are used.     

What is wrong about Robocops as consultants? A technology-centric critique of predictive policing

Fighting crime has historically been a field that drives technological innovation, and it can serve as an example of different governance styles in societies. Predictive policing is one of the recent innovations that covers technical trends such as machine learning, preventive crime fighting strategies, and actual policing in cities. However, it seems that a combination of exaggerated hopes produced by technology evangelists, media hype, and ignorance of the actual problems of the technology may have (over-)boosted sales of software that supports policing by predicting offenders and crime areas. In this paper we analyse currently used predictive policing software packages with respect to common problems of data mining, and describe challenges that arise in the context of their socio-technical application.     

Rapid reaction of nanomolar Mn(II) with superoxide radical in seawater and simulated freshwater

Superoxide radical (O2-) has been proposed to be an important participant in oxidation-reduction reactions of metal ions in natural waters. Here, we studied the reaction of nanomolar Mn(II) with O2- in seawater and simulated freshwater, using chemiluminescence detection of O2- to quantify the effect of Mn(II) on the decay kinetics of O2-. With 3-24 nM added [Mn(II)] and <0.7 nM [O2-], we observed effective second-order rate constants for the reaction of Mn(II) with O2- of 6×10(6) to 1×10(7) M(-1)·s(-1) in various seawater samples. In simulated freshwater (pH 8.6), the effective rate constant of Mn(II) reaction with O2- was somewhat lower, 1.6×10(6) M(-1)·s(-1). With higher initial [O2-], in excess of added [Mn(II)], catalytic decay of O2- by Mn was observed, implying that a Mn(II/III) redox cycle occurred. Our results show that reactions with nanomolar Mn(II) could be an important sink of O2- in natural waters. In addition, reaction of Mn(II) with superoxide could maintain a significant fraction of dissolved Mn in the +III oxidation state.     

Phytogenic pigments in animal nutrition: potentials and risks

Phytogenic pigments are secondary plant compounds responsible for coloring effects in plant tissues. In particular, phenolic flavonoids and terpenoid carotenoids, but also rare compounds like curcumin and betalain, form this group of biochemical agents used in animal nutrition. From the perspective of ecological mutuality between plants and animals, these compounds are of crucial importance because they serve as visual attraction for herbivores but also signal nutritional and/or health‐promoting values. This review focuses on the properties of phytogenic pigments which are likely to impact feed intake and preferences of livestock. Also natural prophylactic and/or therapeutic properties and, in particular, the potential of pigments to enhance quality and health value of animal products for human consumption are important issues. Nevertheless, reasonable limits of use due to possible adverse indications have been suggested recently. Pathways of digestion, metabolism and excretion in animals play a crucial role not only in the evaluation of effectiveness but also in the prediction of potential risks for human consumption. The popularity of natural feed additives is growing; therefore, more research work is needed to better understand metabolic pathways in the animal's body and to better estimate the potentials and risks of pigmenting plant compounds used in animal nutrition. © 2015 Society of Chemical Industry     

γ-戊酮酸丁酯反应精馏过程的逐步优化方案设计

Butyl-levulinate has been identified as a promising fuel candidate with high oxygen content. Its combustion in diesel engines yields very low soot and NOx emissions. It can be produced by the esterification of butanol and levulinic acid, which themselves are platform chemicals in a biorenewables-based chemical supply chain. Since the equilibrium of esterification limits the conversion in a conventional reactor, reactive distillation can be applied to overcome this limitation. The presence of the high-boiling catalyst sulfuric acid requires a further separation step downstream of the reactive distillation column to recover the catalyst for recycle. Optimal design specifications and an optimal operating point are determined using rigorous flowsheet optimization. The challenging optimization problem is solved by a favorable initialization strategy and continuous reformulation. The design identified has the potential to produce a renewable transportation fuel at reasonable cost.