Comparative analysis of the oil and supercritical CO2 extract of Ridolfia segetum (L.) Moris

Supercritical carbon dioxide extraction allowed to obtain the volatile oil of different aerial parts of Ridolfia segetum (L.) Moris. Extraction conditions were as follows: pressure, 90 bar; temperature, 50 degrees C and carbon dioxide flow, Phi = 1.0 kg h(-1). Waxes were entrapped in the first separator set at 90 bar and -10 degrees C. The oil was recovered in the second separator working at 15 bar and 10 degrees C. The main components of the flower oil were alpha-phellandrene (19.4%), terpinolene (20.5%), piperitenone oxide (11.6%), beta-phellandrene (8.2%), (Z)-beta-ocimene (7.8%), myristicin (7.5%) and p-cymene (4.4%). The comparison with the hydrodistilled (HD) oil reveal that the significative difference was the content of sesquiterpenes which are higher in the supercritical fluid extraction (SFE) products. Collection of samples at different extraction times during supercritical extraction, allowed to monitor the change of the oil composition. Lighter compounds, as hydrocarbon monoterpenes, were extracted in shorter times than the heavier hydrocarbon and oxygenated sesquiterpenes. The oil from the steams was characterized by a high content of alpha-phellandrene (12.9%), terpinolene (11.6%), myristicin (11.0%), p-cymene (9.9%), beta-phellandrene (8.2%) and (Z)-beta-ocimene (6.0%) while the main components of the fruits were found to be myristicin (70.8%), piperitenone oxide (19.9%) and dill apiole (4.2%).     

Chymotrypsin immobilization on epoxy monolithic silica columns: development and characterization of a bioreactor for protein digestion

The preparation and optimization of a new monolithic chymotrypsin bioreactor for online protein digestion is described. Silica monolithic supports have been activated with epoxide functionalities following an optimized in situ procedure and used for covalent immobilization of chymotrypsin in one-step reaction under different conditions. A total of four bioreactors were prepared and characterized in terms of the amount of immobilized enzyme and apparent active units by using a standard substrate, N-benzoyl-L-tyrosine p-nitroanilide (BTPNA). The stability of the bioreactors was evaluated and the morphology of the support after immobilization and use was studied by SEM analysis. The proteolytic activity of the optimized chymotrypsin bioreactor was evaluated using HSA as a model protein by online coupling of the bioreactor with LC-ESI-MS. With the online protocol, complete protein digestion in 120 min was achieved with a sequence coverage of 97.3%.     

Swimming against the Stream? A Discussion of the Bonding in d6 and d8 Fluoro Complexes and Its Consequences for Catalytic Applications

Fluoride has recently found increasing application as coligand both in complexes of late transition metals and as a reagent in asymmetric catalysis. In recent papers, this topic was reviewed, with emphasis on the role played by so‐called ‘push‐pull interactions' between the fluoro ligand and a π acid in the stabilization of fluoro complexes with a d⁶ or d⁸ electron configuration. This picture has led to the concept that fluoride is the strongest π‐donor in the halide series. Herein, the latter concept is discussed and criticized. In particular, the effect of the ionicity of the metal‐fluoride bond is proposed as an alternative explanation to most of the observations that show a ‘reversed' halide order. The ionic character of the M F bond also accounts for its intrinsic reactivity and suggests some strategies for the stabilizatioin of fluoro complexes, including the use of coordinative unsaturation. The scope and limitations of the application of d⁶ and d⁸ fluoro complexes in catalysis are also discussed. The most promising application is the use of 16‐electron fluoro complexes in the metal‐promoted formation of the C F bond.     

The Significance of Metal Coordination in Imidazole-Functionalized Metal–Organic Frameworks for Carbon Dioxide Utilization

The grafting of imidazole species onto coordinatively unsaturated sites within metal–organic framework MIL-101(Cr) enables enhanced CO₂ capture in close proximity to catalytic sites. The subsequent combination of CO₂ and epoxide binding sites, as shown through theoretical findings, significantly improves the rate of cyclic carbonate formation, producing a highly active CO₂ utilization catalyst. An array of spectroscopic investigations, in combination with theoretical calculations reveal the nature of the active sites and associated catalytic mechanism which validates the careful design of the hybrid MIL-101(Cr).     

gem-Diethyl Pyrroline Nitroxide Spin Labels: Synthesis,EPR Characterization,Rotamer Libraries and Biocompatibility

The availability of bioresistant spin labels is crucial for the optimization of site-directed spin labeling protocols for EPR structural studies of biomolecules in a cellular context. As labeling can affect proteins’ fold and/or function, having the possibility to choose between different spin labels will increase the probability to produce spin-labeled functional proteins. Here, we report the synthesis and characterization of iodoacetamide- and maleimide-functionalized spin labels based on the gem-diethyl pyrroline structure. The two nitroxide labels are compared to conventional gem-dimethyl analogs by site-directed spin labeling (SDSL) electron paramagnetic resonance (EPR) spectroscopy, using two water soluble proteins: T4 lysozyme and Bid. To foster their use for structural studies, we also present rotamer libraries for these labels, compatible with the MMM software. Finally, we investigate the “true” biocompatibility of the gem-diethyl probes comparing the resistance towards chemical reduction of the NO group in ascorbate solutions and E. coli cytosol at different spin concentrations.     

Tuning the Electrochemical Properties of Novel Asymmetric Integral Sulfonated Polysulfone Cation Exchange Membranes

In this study, novel asymmetric integral cation exchange membranes were prepared by the wet phase inversion of sulfonated polysulfone (SPSf) solutions. SPSf with different degrees of sulfonation (DS) was synthesized by variation in the amount of chlorosulfonic acid utilized as a sulfonating agent. The characterization of SPSf samples was performed using FTIR and ¹H-NMR techniques. SPSf with a DS of 0.31 (0.67 meq/g corresponding ion exchange capacity) was chosen to prepare the membranes, as polymers with a higher DS resulted in poor mechanical properties and excessive swelling in water. By a systematic study, the opportunity to tune the properties of SPSf membranes by acting on the composition of the polymeric solution was demonstrated. The effect of two different phase inversion parameters, solvent type and co-solvent ratio, were investigated by morphological and electrochemical characterization. The best properties (permselectivity of 0.86 and electrical resistance of 6.3 Ω∙cm²) were obtained for the membrane prepared with 2-propanol (IPA):1-Methyl-2-pyrrolidinone (NMP) in a 20:80 ratio. This membrane was further characterized in different solution concentrations to estimate its performance in a Reverse Electrodialysis (RED) operation. Although the estimated generated power was less than that of the commercial CMX (Neosepta) membrane, used as a benchmark, the tailor-made membrane can be considered as a cost-effective alternative, as one of the main limitations to the commercialization of RED is the high membrane price.     

Optimising for energy or robustness? Trade-offs for VM consolidation in virtualized datacenters under uncertainty

Reducing the energy consumption of virtualized datacenters and the Cloud is very important in order to lower CO\( _2 \) footprint and operational cost of a Cloud operator. However, there is a trade-off between energy consumption and perceived application performance. In order to save energy, Cloud operators want to consolidate as many Virtual Machines (VM) on the fewest possible physical servers, possibly involving overbooking of resources. However, that may involve SLA violations when many VMs run on peak load. Such consolidation is typically done using VM migration techniques, which stress the network. As a consequence, it is important to find the right balance between the energy consumption and the number of migrations to perform. Unfortunately, the resources that a VM requires are not precisely known in advance, which makes it very difficult to optimise the VM migration schedule. In this paper, we therefore propose a novel approach based on the theory of robust optimisation. We model the VM consolidation problem as a robust Mixed Integer Linear Program and allow to specify bounds for e.g. resource requirements of the VMs. We show that, by using our model, Cloud operators can effectively trade-off uncertainty of resource requirements with total energy consumption. Also, our model allows us to quantify the price of the robustness in terms of energy saving against resource requirement violations.