Synthesis and Coordination of Bicyclic Phosphorus-Nitrogen Ligands

<p>This thesis describes the synthesis and coordination chemistry of bicyclic phosphorus-nitrogen (PN) ligands containing the rigid and preorganised bicyclo[3.3.1]nonan-9-one framework. The PN ligands were prepared via the Mannich condensation reaction of four different phosphorinanone classes with amines and aldehydes. The phosphorinanone compounds, 2,6-dimethyl-3,5-diphenyl-4-phenyl-4- phosphacyclohexanone (isomers 50 and 51), 3,5-diphenyl-4-phenyl-4- phosphacyclohexanone (44, 45) and 4-phenyl-4-phosphacyclohexanone (42) were prepared by literature methods, whereas the isomers of 4-t-butyl-2,6- di(carbomethoxy) - 3,5 - bis(p - dimethylaminophenyl) - 4 - phosphacyclohexanone (53, 54) were synthesised by the reaction of ButPH2 with 2,4-di(carbomethoxy)- 1,5 - bis(p - dimethylaminophenyl)penta - 1,4 - dien - 3 - one (38). The Mannich reactions of phosphorinanones 50 and 51 were not successful, whereas the reactions of 44, 45 and 42 produced unidentifiable products. The reaction of phosphorinanone 53 with methylamine and formaldehyde produced the bicyclic PN compound 7-t-butyl-1,5-di(carbomethoxy)-6,8-bis(p-dimethylaminophenyl)- 3 - methyl - 3 - aza - 7 - phosphabicyclo[3.3.1]nonan - 9 - one (65). The identical Mannich reaction of phosphorinanone 54 also yielded 65, as well as the PN compound 4-t-butyl-6-carbomethoxy-5-(p-dimethylaminophenyl)- 2-methyl-2-aza-4-phosphacyclohexanone (66) and the E/Z isomers of 3-(p-dimethylaminophenyl)methyl-2-propenoate (67). The bicyclic PN ligand 65 adopts a chair-chair conformation in solution and the solid state as confirmed by X-ray crystallography. The coordination chemistry of this ligand was comprehensively explored with rhodium, palladium and platinum, and a wide range of complexes were synthesised including [ML2(65)] (M = Pd, Pt; L = Cl, Me), [ML(65)] (M = Rh, Pd, Pt; L = C2H4, cod, dba, norb) (cod = cycloocta-1,5-diene, dba = trans,trans- dibenzylideneacetone, norb = norborn-2-ene), [Pd(n3 -C3H5)(65)]X (X = Cl, SbF6) and [PtL(65)]CH(SO2CF3)2 (L = 1-o,4-5-n-C8H13, 1-3-n-C8H13). Cycloplatination at the ortho-position of the 6,8-dimethylaminophenyl sub- stituents was an interesting feature of the coordination chemistry of PN ligand 65. Ortho-metallation at both dimethylaminophenyl groups led to the formation of complex [Pt(C2H4)(65-2H)] (76), whereas metallation of only one aryl group produced the complex [Pt(C8H13)(65-H)] (87). Further reaction of complex 76 yielded the trans- and cis-hydroxo-bridged dimers [Pt2(u-OH)2(65-H)2] (98, 101). The nitrogen donor atom is not coordinated to the platinum metal centres in the cyclometallated PN complexes. Protonation of [Pt(C2H4)(65)] (75) with CH2(SO2CF3)2 produced the hydride complex [PtH{CH(SO2CF3)2}(65)] (92) and the agostic ethyl complex [Pt(C2H5)(65)]CH(SO2CF3)2 (93). Similarly, protonation of [Pt(norb)(65)] (74) with CHPh(SO2CF3)2 gave the norbornyl agostic complex [Pt(C7H11)(65)]CPh(SO2CF3)2 (94) as confirmed by X-ray crystallography. In addition, hydrated analogues of some of the coordination complexes of PN ligand 65 mentioned previously were also observed. In such complexes, the central carbonyl group at position 9 was hydrated to form a geminal diol. The hydrated complexes exhibited similar chemical characteristics to their ketone counterparts. The 15N NMR chemical shifts of the nitrogen donor atom in PN ligand 65 and its various metal complexes were obtained from inversely-detected 1H- 15N HMBC experiments. The NMR data showed no explicit relationship between the coordination mode of the nitrogen group and the 15N chemical shift.</p>

Synthesis and Coordination of Bicyclic Phosphorus-Nitrogen Ligands

<p>This thesis describes the synthesis and coordination chemistry of bicyclic phosphorus-nitrogen (PN) ligands containing the rigid and preorganised bicyclo[3.3.1]nonan-9-one framework. The PN ligands were prepared via the Mannich condensation reaction of four different phosphorinanone classes with amines and aldehydes. The phosphorinanone compounds, 2,6-dimethyl-3,5-diphenyl-4-phenyl-4- phosphacyclohexanone (isomers 50 and 51), 3,5-diphenyl-4-phenyl-4- phosphacyclohexanone (44, 45) and 4-phenyl-4-phosphacyclohexanone (42) were prepared by literature methods, whereas the isomers of 4-t-butyl-2,6- di(carbomethoxy) - 3,5 - bis(p - dimethylaminophenyl) - 4 - phosphacyclohexanone (53, 54) were synthesised by the reaction of ButPH2 with 2,4-di(carbomethoxy)- 1,5 - bis(p - dimethylaminophenyl)penta - 1,4 - dien - 3 - one (38). The Mannich reactions of phosphorinanones 50 and 51 were not successful, whereas the reactions of 44, 45 and 42 produced unidentifiable products. The reaction of phosphorinanone 53 with methylamine and formaldehyde produced the bicyclic PN compound 7-t-butyl-1,5-di(carbomethoxy)-6,8-bis(p-dimethylaminophenyl)- 3 - methyl - 3 - aza - 7 - phosphabicyclo[3.3.1]nonan - 9 - one (65). The identical Mannich reaction of phosphorinanone 54 also yielded 65, as well as the PN compound 4-t-butyl-6-carbomethoxy-5-(p-dimethylaminophenyl)- 2-methyl-2-aza-4-phosphacyclohexanone (66) and the E/Z isomers of 3-(p-dimethylaminophenyl)methyl-2-propenoate (67). The bicyclic PN ligand 65 adopts a chair-chair conformation in solution and the solid state as confirmed by X-ray crystallography. The coordination chemistry of this ligand was comprehensively explored with rhodium, palladium and platinum, and a wide range of complexes were synthesised including [ML2(65)] (M = Pd, Pt; L = Cl, Me), [ML(65)] (M = Rh, Pd, Pt; L = C2H4, cod, dba, norb) (cod = cycloocta-1,5-diene, dba = trans,trans- dibenzylideneacetone, norb = norborn-2-ene), [Pd(n3 -C3H5)(65)]X (X = Cl, SbF6) and [PtL(65)]CH(SO2CF3)2 (L = 1-o,4-5-n-C8H13, 1-3-n-C8H13). Cycloplatination at the ortho-position of the 6,8-dimethylaminophenyl sub- stituents was an interesting feature of the coordination chemistry of PN ligand 65. Ortho-metallation at both dimethylaminophenyl groups led to the formation of complex [Pt(C2H4)(65-2H)] (76), whereas metallation of only one aryl group produced the complex [Pt(C8H13)(65-H)] (87). Further reaction of complex 76 yielded the trans- and cis-hydroxo-bridged dimers [Pt2(u-OH)2(65-H)2] (98, 101). The nitrogen donor atom is not coordinated to the platinum metal centres in the cyclometallated PN complexes. Protonation of [Pt(C2H4)(65)] (75) with CH2(SO2CF3)2 produced the hydride complex [PtH{CH(SO2CF3)2}(65)] (92) and the agostic ethyl complex [Pt(C2H5)(65)]CH(SO2CF3)2 (93). Similarly, protonation of [Pt(norb)(65)] (74) with CHPh(SO2CF3)2 gave the norbornyl agostic complex [Pt(C7H11)(65)]CPh(SO2CF3)2 (94) as confirmed by X-ray crystallography. In addition, hydrated analogues of some of the coordination complexes of PN ligand 65 mentioned previously were also observed. In such complexes, the central carbonyl group at position 9 was hydrated to form a geminal diol. The hydrated complexes exhibited similar chemical characteristics to their ketone counterparts. The 15N NMR chemical shifts of the nitrogen donor atom in PN ligand 65 and its various metal complexes were obtained from inversely-detected 1H- 15N HMBC experiments. The NMR data showed no explicit relationship between the coordination mode of the nitrogen group and the 15N chemical shift.</p>

Technical fishway passage structures provide high passage efficiency and effective passage for adult Pacific salmonids at eight large dams

Fishways have been widely used for upstream passage around human-built structures, but ‘success’ has varied dramatically. Evaluation of fishway success has typically been conducted at local scales using metrics such as fish passage efficiency and passage time, but evaluations are increasingly used in broader assessments of whether passage facilities meet population-specific conservation and management objectives. Over 15 years, we monitored passage effectiveness at eight dams on the Columbia and Snake rivers for 26,886 radio-tagged spring-summer and fall Chinook Salmon O. tshwaytscha, Sockeye Salmon O. nerka, and summer steelhead O. mykiss during their migrations to spawning sites. Almost all fish that entered dam tailraces eventually approached and entered fishways. Tailrace-to-forebay passage efficiency estimates at individual dams were consistently high, averaging 0.966 (SD = 0.035) across 245 run×year×dam combinations. These estimates are among the highest recorded for any migratory species, which we attribute to the scale of evaluation, salmonid life history traits (e.g., philopatry), and a sustained adaptive management approach to fishway design, maintenance, and improvement. Full-dam fish passage times were considerably more variable, with run×year×dam medians ranging from 5–65 h. Evaluation at larger scales provided evidence that fishways were biologically effective, e.g., we observed rapid migration rates (medians = 28–40 km/d) through river reaches with multiple dams and estimated fisheries-adjusted upstream migration survival of 67–69%. However, there were substantive uncertainties regarding effectiveness. Uncertainty about natal origins confounded estimation of population-specific survival and interpretation of apparent dam passage ‘failure’, while lack of post-migration reproductive data precluded analyses of delayed or cumulative effects of passing the impounded system on fish fitness. Although the technical fishways are effective for salmonids in the Columbia-Snake River system, other co-migrating species have lower passage rates, highlighting the need for species-specific design and evaluation wherever passage facilities impact fish management and conservation goals.

Thermally-actuated microfluidic membrane valve for point-of-care applications

Microfluidics has enabled low volume biochemistry reactions to be carried out at the point-of-care. A key component in microfluidics is the microfluidic valve. Microfluidic valves are not only useful for directing flow at intersections but also allow mixtures/dilutions to be tuned real-time and even provide peristaltic pumping capabilities. In the transition from chip-in-a-lab to lab-on-a-chip, it is essential to ensure that microfluidic valves are designed to require less peripheral equipment and that they are transportable. In this paper, a thermally-actuated microfluidic valve is presented. The valve itself is fabricated with off-the-shelf components without the need for sophisticated cleanroom techniques. It is shown that multiple valves can be controlled and operated via a power supply and an Arduino microcontroller; an important step towards transportable microfluidic devices capable of carrying out analytical assays at the point-of-care. It is been calculated that a single actuator costs less than $1, this highlights the potential of the presented valve for scaling out. The valve operation is demonstrated by adjusting the ratio of a water/dye mixture in a continuous flow microfluidic chip with Y-junction channel geometry. The power required to operate one microfluidic valve has been characterised both theoretically and experimentally. Cyclical operation of the valve has been demonstrated for 65 h with 585 actuations. The presented valve is capable of actuating rectangular microfluidic channels of 500 μm × 50 μm with an expected temperature increase of up to 5 °C. The fastest actuation times achieved were 2 s for valve closing (heating) and 9 s for valve opening (cooling).

Epileptiform Discharge and Electrographic Seizures during the Hypothermia Phase as Predictors of Rewarming Seizures in Children after Resuscitation

The aim of this study was to determine the frequency, timing, and predictors of rewarming seizures in a cohort of children undergoing therapeutic hypothermia after resuscitation. We retrospectively reviewed consecutive pediatric patients undergoing therapeutic hypothermia after resuscitation admitted to our pediatric intensive care unit between January 2000 and December 2019. Continuous electroencephalographic monitoring was performed during hypothermia (24 h for cardiac aetiologies and 72 h for asphyxial aetiologies), rewarming (72 h), and then an additional 12 h of normothermia. Thirty comatose children undergoing therapeutic hypothermia after resuscitation were enrolled, of whom 10 (33.3%) had rewarming seizures. Two (20%) of these patients had their first seizure during the rewarming phase. Four (40%) patients had electroclinical seizures, and six (60%) had nonconvulsive seizures. The median time from starting rewarming to the onset of rewarming seizures was 37.3 h (range 6 to 65 h). The patients with interictal epileptiform activity and electrographic seizures during the hypothermia phase were more likely to have rewarming seizures compared to those without interictal epileptiform activity or electrographic seizures (p = 0.019 and 0.019, respectively). Therefore, in high-risk patients, continuous electroencephalographic monitoring for a longer duration may help to detect rewarming seizures and guide clinical management.

Phase Space Analysis of Pig Ear Skin Temperature during Air and Road Transport

High or variable ambient temperature can affect thermal regulation in livestock, but few studies have studied thermal variability during air and road transport, partly due to the lack of tools to compare thermal data from a long time series over periods of different duration. In this study, we recorded the ear skin temperature (EST) of 11 Duroc breeder pigs (7 females and 4 males) during commercial intercontinental transport from Canada to Spain, which included both road and aircraft travel and lasted 65 h. The EST was measured using a logger placed inside the left ear. Phase space diagrams EST, that is EST time series vs. itself delayed in time, were used to quantify the variability of the time-temperature series based on the areas that included all the points in the phase space. Phase space areas were significantly higher for all the animals during air travel, almost doubling that of road transport. Using the phase spaces, we identified an event during air transport that lasted 57 min, leading to a general decrease in EST by 8 °C, with respect to the average EST (34.1 °C). We also found that thermal variability was more stable in males (F = 20.81, p = 0.0014), which were also older and heavier.

In Situ Creep Behavior Characterization of Single Crystal Superalloy by UV-DIC at 980 °C

High temperature creep resistance is a critical characteristic of Ni-based single crystal (SX) superalloys. In this work, the creep behavior of a Ni-based SX superalloy was in situ characterized at 980 °C by ultraviolet (UV) imaging combined two-dimensional digital image correlation (DIC) in vacuum environment. The surface pattern was fabricated to maintain stable over 65 h at 980 °C. The pattern images captured by UV imaging were analyzed using mean gray value and the full-field strain map of creep deformation was obtained. A laser displacement senor (LDS) was employed for measuring the creep strain on the specimen for comparison. The creep deformation result shows a good agreement between DIC and LDS, the microstructure of the different creep areas on the specimens also demonstrate that the results of DIC are reliable. The in situ creep characterization by UV-DIC shows a great potential for investigating creep behaviors at high temperatures.

Satellite-Based Reconstruction of the Volcanic Deposits during the December 2015 Etna Eruption

Satellite-derived data, including an estimation of the eruption rate, proximal volcanic deposits and lava flow morphometric parameters (area, maximum length, thickness, and volume) are provided for the eruption that occurred at Mt Etna on 6–8 December 2015. This eruption took place at the New Southeast Crater (NSEC), the youngest of the summit craters of Etna, shortly after a sequence of four violent paroxysmal events took place in 65 h (3–5 December) at “Voragine”, the oldest summit crater. Multispectral SEVIRI images at 15 min sampling time have been used to compute time-averaged eruption rate curves, while tri-stereo Pléiades images, at 50 cm spatial resolution, provided the pre-eruptive topography and topographic changes due to volcanic deposits. In addition to the two types of satellite data, other parameters have been inferred, such as probable vesicularity and pyroclastic deposits.

Seed Viability of Heracleum mantegazzianum (Apiaceae) Is Quickly Reduced at Temperatures Prevailing in Biogas Plants

Heracleum mantegazzianum is an invasive plant species with enormous effect on ecosystems and human health. Mechanical weed management often results in large amounts of biomass. Fermentation in biogas plants can be used for disposal of this biomass contaminated with seeds and for energetic utilization, if spreading of viable seeds with fermentation residues is prevented. Our aim is to quantify the risk of seed survival in mesophilic biogas plants. Seeds were harvested at three ripening stages in central Germany. They were incubated for 0, 0.5, 1, 2, 4, and 8 days at 35 and 42 °C in water baths. Thereafter, seed viability was assessed by a tetrazolium test. Furthermore, germinative capacity of seeds which had passed an incubation of 48 h at 35 °C were tested. After eight days in water bath none of the 1199 tested seeds were viable anymore. The time until half of the seeds died (ED50) ranged from 9 to 65 h, whereby high temperature accelerated the mortality. Germinative capacity was similar to the seed survival rate. The results suggest that fermentation of H. mantegazzianum biomass poses only a low risk of viable seed spread, if the operating temperature of the biogas plant achieves 42 °C and a high retention time is ensured.

Expression and Characterization of a Dye-Decolorizing Peroxidase from Pseudomonas Fluorescens Pf0-1

The consumption of dyes is increasing worldwide in line with the increase of population and demand for clothes and other colored products. However, the efficiency of dyeing processes is still poor and results in large amounts of colored effluents. It is desired to develop a portfolio of enzymes which can be used for the treatment of colored wastewaters. Herein, we used genome sequence information to discover a dye-decolorizing peroxidase (DyP) from Pseudomonas fluorescens Pf-01. Two genes putatively encoding for DyPs were identified in the respective genome and cloned for expression in Escherichia coli, of which one (PfDyP B2) could be overexpressed as a soluble protein. PfDyP B2 shows some typical features known for DyPs which includes the ability to convert dyes at the expense of hydrogen peroxide. Interestingly, t-butyl hydroperoxide could be used as an alternative substrate to hydrogen peroxide. Immobilization of PfDyP B2 in calcium-alginate beads resulted in a significant increase in stability: PfDyP B2 retains 80% of its initial activity after 2 h incubation at 50 °C, while the soluble enzyme is inactivated within minutes. PfDyP B2 was also tested with aniline and ethyl diazoacetate as substrates. Based on GC-MS analyses, 30% conversion of the starting material was achieved after 65 h at 30 °C. Importantly, this is the first report of a DyP-catalyzed insertion of a carbene into an N-H bond.