Classifying Ecosystem Services for Economic Valuation: The case of forest water services

30 p.

A unified strategy to ent-kauranoid natural products : total syntheses of (–)-maoecrystal Z, (–)-trichorabdal A, and (–)-longikaurin E

The diterpenoid constituents of the Isodon plants have attracted reasearchers interested in both their chemical structures and biological properties for more than a half-century. In recent years, the isolations of new members displaying previously unprecedented ring systems and highly selective biological properties have piqued interest from the synthetic community in this class of natural products.

Reported herein is the first total synthesis of such a recently isolated diterpenoid, (–)-maoecrystal Z. The principal transformations implemented in this synthesis include two highly diastereoselective radical cyclization reactions: a Sm^(II)-mediated reductive cascade cyclization, which forms two rings and establishes four new stereocenters in a single step, and a Ti^(III)-mediated reductive epoxide-acrylate coupling that yields a functionalized spirolactone product, which forms a core bicycle of maoecrystal Z.

The preparation of two additional ent-kauranoid natural products, (–)-trichorabdal A and (–)-longikaurin E, is also described from a derivative of this key spirolactone. These syntheses are additionally enabled by the palladium-mediated oxidative cyclization reaction of a silyl ketene acetal precursor that is used to install the bridgehead all-carbon quaternary stereocenter and bicyclo[3.2.1]octane present in each natural product. These studies have established a synthetic relationship among three architecturally distinct ent-kaurane diterpenoids and have forged a path for the preparation of interesting unnatural ent-kauranoid structural analogs for more thorough biological study.

The development of an asymmetric palladium-catalyzed conjugate addition and its application toward the total syntheses of taiwaniaquinoid natural products

The asymmetric synthesis of quaternary stereocenters remains a challenging problem in organic synthesis. Past work from the Stoltz laboratory has resulted in methodology to install quaternary stereocenters α- or γ- to carbonyl compounds. Thus, the asymmetric synthesis of β-quaternary stereocenters was a desirable objective, and was accomplished by engineering the palladium-catalyzed addition of arylmetal organometallic reagents to α,β-unsaturated conjugate acceptors.

Herein, we described the rational design of a palladium-catalyzed conjugate addition reactions utilizing a catalyst derived from palladium(II) trifluoroacetate and pyridinooxazole ligands. This reaction is highly tolerant of protic solvents and oxygen atmosphere, making it a practical and operationally simple reaction. The mild conditions facilitate a remarkably high functional group tolerance, including carbonyls, halogens, and fluorinated functional groups. Furthermore, the reaction catalyzed conjugate additions with high enantioselectivity with conjugate acceptors of 5-, 6-, and 7-membered ring sizes. Extension of the methodology toward the asymmetric synthesis of flavanone products is presented, as well.

A computational and experimental investigation into the reaction mechanism provided a stereochemical model for enantioinduction, whereby the α-methylene protons adjacent the enone carbonyl clashes with the tert-butyl groups of the chiral ligand. Additionally, it was found that the addition of water and ammonium hexafluorophosphate significantly increases the reaction rate without sacrificing enantioselectivity. The synergistic effects of these additives allowed for the reaction to proceed at a lower temperature, and thus facilitated expansion of the substrate scope to sensitive functional groups such as protic amides and aryl bromides. Investigations into a scale-up synthesis of the chiral ligand (S)-tert-butylPyOx are also presented. This three-step synthetic route allowed for synthesis of the target compound of greater than 10 g scale.

Finally, the application of the newly developed conjugate addition reaction toward the synthesis of the taiwaniaquinoid class of terpenoid natural products is discussed. The conjugate addition reaction formed the key benzylic quaternary stereocenter in high enantioselectivity, joining together the majority of the carbons in the taiwaniaquinoid scaffold. Efforts toward the synthesis of the B-ring are presented.

Modeling the Links between Biodiversity, Ecosystem Services and Human Wellbeing in the Context of Climate Change: Results from an Econometric Analysis on the European Forest Ecosystems

25 p.

The search for gravitational waves from the coalescence of black hole binary systems in data from the LIGO and Virgo detectors. Or: A dark walk through a random forest

The LIGO and Virgo gravitational-wave observatories are complex and extremely sensitive strain detectors that can be used to search for a wide variety of gravitational waves from astrophysical and cosmological sources. In this thesis, I motivate the search for the gravitational wave signals from coalescing black hole binary systems with total mass between 25 and 100 solar masses. The mechanisms for formation of such systems are not well-understood, and we do not have many observational constraints on the parameters that guide the formation scenarios. Detection of gravitational waves from such systems — or, in the absence of detection, the tightening of upper limits on the rate of such coalescences — will provide valuable information that can inform the astrophysics of the formation of these systems. I review the search for these systems and place upper limits on the rate of black hole binary coalescences with total mass between 25 and 100 solar masses. I then show how the sensitivity of this search can be improved by up to 40% by the the application of the multivariate statistical classifier known as a random forest of bagged decision trees to more effectively discriminate between signal and non-Gaussian instrumental noise. I also discuss the use of this classifier in the search for the ringdown signal from the merger of two black holes with total mass between 50 and 450 solar masses and present upper limits. I also apply multivariate statistical classifiers to the problem of quantifying the non-Gaussianity of LIGO data. Despite these improvements, no gravitational-wave signals have been detected in LIGO data so far. However, the use of multivariate statistical classification can significantly improve the sensitivity of the Advanced LIGO detectors to such signals.

Ecological aspects of New Forest streams, draining one of Britain's unique areas

This article describes the streams of this unique area of Britain and reviews the published and some unpublished information that is currently available. None of the rivers in the New Forest are more than 30 km long. Many reaches have been artificially straightened, channelized and regraded since the 1840's. The stream waters are typically base-poor, with low nutrient concentrations. Primary productivity and standing crops of algae are predictably low when compared with other streams carrying higher concentrations of minerals and nutrients. The earliest records on the macroinvertebrate fauna go back to the late 19th Century. By 1940, over 20 species of Trichoptera and 10 species of Plecoptera had been recorded, but only four species of Ephemeroptera. Twenty species of fish occur in the streams of the New Forest of which the most common are brown trout, minnow, bullhead, stone loach, brook lamprey and eel.

Rapid changes in the vegetation of a shallow pond in Epping Forest, related to recent droughts

Over much of Britain, 1995 and 1996 have been perceived as drought years. To evaluate the impact that local climatic conditions are having upon successional changes in higher vegetation (macrophytes), Speakmans Pond in Epping Forest was surveyed and mapped in 1996. The results are related to previous vegetation surveys carried out in 1989 and 1991. In 1989 the dominant marginal vegetation was floating sweet-grass Glyceria fluitans, which also covered a major part of the main body of the pond. Other abundant species included soft rush Juncus effusus, reed mace Typha latifolia and yellow flag Iris pseudocorus. A small (central) area of open water contained bladderwort Utricularia vulgaris and white water-lily Nymphaea alba. A similar plant coverage was found in 1991, with a dominance of floating sweet-grass along the shallow eastern edge. A marked change in the pond was found during the 1996 survey of vegetation in July, when the pool was dry. The major plant cover now consisted of creeping bent Agrostis stolonifera, with isolated clumps of Yorkshire fog Holcus lanatus around the edges; both are terrestrial grasses found on land surrounding the pond. Rushes (Juncus) had increased their distribution round the margins of the pond, and the patch of yellow flag noted in 1989 and 1991 was not found in 1996. The deeper trenches were also dry, but a small patch of white water-lily remained adjacent to one of the trenches.

A note on the shallow ponds on the gravel ridge of Epping Forest, Essex

In a recent study in Freshwater Forum on Speakman's Pond (also known as Nursery Pond) the impression was given that it had been a permanent water-filled pond which had recently dried out due to exceptionally low rainfall. In fact, Nursery Pond was created by the extraction of gravel and was never more than 50 cm deep, until the creation of trenches in 1989 to provide a refuge for aquatic life. The Nursery Pond followed a seasonal pattern of filling with winter rain and slowly drying out between 1940 to 1970. It had no established aquatic vegetation, no fish, and only rarely amphibians. Permanent water was present only from about 1979 until 1995 due to leakage from a Thames water storage reservoir.

Comparative limnology of waters in a coniferous forest: is a generalisation possible?

The high density of meres and mosses in the Delamere area comes from numerous moraine-hollows formed after the melting of stranded ice-blocks following last glaciation. The main vegetation is of conifers along with some deciduous species and the area was designated as a National Forest Park in 1987. It has been managed since the beginning of the 19th century and is a popular tourist area with walking, orienteering, cycling and educational activities. In recent years this forest park has been attracting over half a million people per year. This paper studies the limnology of different aquatic habitats in the Delamere Forest area in order to give some insight into the waters of a coniferous, temperate forest area, which has so far been largely unexplored. The authors assume therefore, thought that despite apparent large variability in origin, age, surface area, morphometry, catchment size and hydraulic regime, the waters of Delamere Forest might share some revealing chemical and biological features. Seven water-bodies in the Delamere Forest Park area, namely, Black Lake, Blakemere Moss, Delamere Lake, Delamere Quarry, Hatchmere, Windyhowe Farm Spring and Fir Brook were sampled, their water chemistry and dissolved organic carbon and the occurrence of phytoplankton and zooplankton species examined. In a final chapter the authors analyse their findings for patterns.

Applications of a Concise and General Strategy for the Syntheses of Transtaganolide and Basiliolide Natural Products

Herein are described the total syntheses of all members of the transtaganolide and basiliolide natural product family. Utilitzation of an Ireland–Claisen rearrangement/Diels–Alder cycloaddition cascade (ICR/DA) allowed for rapid assembly of the transtaganolide and basiliolide oxabicyclo[2.2.2]octane core. This methodology is general and was applicable to all members of the natural product family.

A brief introduction outlines all the synthetic progress previously disclosed by Lee, Dudley, and Johansson. This also includes the initial syntheses of transtaganolides C and D, as well as basiliolide B and epi-basiliolide B accomplished by Stoltz in 2011. Lastly, we discuss our racemic synthesis of basililide C and epi-basiliolide C, which utilized an ICR/DA cascade to constuct the oxabicyclo[2.2.2]octane core and formal [5+2] annulation to form the ketene-acetal containing 7-membered C-ring.

Next, we describe a strategy for an asymmetric ICR/DA cascade, by incorporation of a chiral silane directing group. This allowed for enantioselective construction of the C8 all-carbon quaternary center formed in the Ireland–Claisen rearrangement. Furthermore, a single hydride reduction and subsequent translactonization of a C4 methylester bearing oxabicyclo[2.2.2]octane core demonstrated a viable strategy for the desired skeletal rearrangement to obtain pentacyclic transtaganolides A and B. Application of the asymmetric strategy culminated in the total syntheses of (–)-transtaganolide A, (+)-transtaganolide B, (+)-transtaganolide C, and (–)-transtaganolide D. Comparison of the optical rotation data of the synthetically derived transtaganolides to that from the isolated counterparts has overarching biosynthetic implications which are discussed.

Lastly, improvement to the formal [5+2] annulation strategy is described. Negishi cross-coupling of methoxyethynyl zinc chloride using a palladium Xantphos catalyst is optimized for iodo-cyclohexene. Application of this technology to an iodo-pyrone geranyl ester allowed for formation and isolation of the eneyne product. Hydration of the enenye product forms natural metabolite basiliopyrone. Furthermore, the eneyne product can undergo an ICR/DA cascade and form transtaganolides C and D in a single step from an achiral monocyclic precursor.

Enantioselective Total Synthesis of Diketopiperazinecontaining Natural Products: (–)-Lansai B, (+)-Nocardioazines A and B, and (–)-Acetylapoaranotin

Diketopiperazine (DKP) motif is found in a wide range of biologically active natural products. This work details our efforts toward two classes of DKP-containing natural products.

Class one features the pyrroloindoline structure, derived from tryptophans. Our group developed a highly enantioselective (3 + 2) formal cycloaddition between indoles and acrylates to provide pyrroloindoline products possessing three stereocenters. Utilizing this methodology, we accomplished asymmetric total synthesis of three natural products: (–)-lansai B, (+)-nocardioazines A and B. Total synthesis of (–)-lansai B was realized in six steps, and featured an amino acid dimerization strategy. The total synthesis of (+)-nocardioazine B was also successfully completed in ten steps. Challenges were met in approaching (+)-nocardioazine A, where a seemingly easy last-step epoxidization did not prove successful. After re-examining our synthetic strategy, an early-stage epoxidation strategy was pursued, which eventually yielded a nine-step total synthesis of (+)-nocardioazine A.

Class two is the epidithiodiketopiperazine (ETP) natural products, which possesses an additional episulfide bridge in the DKP core. With the goal of accessing ETPs with different peripheral structures for structure-activity relationship studies, a highly divergent route was successfully developed, which was showcased in the formal synthesis of (–)-emethallicin E and (–)-haematocin, and the first asymmetric synthesis of (–)-acetylapoaranotin.

Study and comparison of four forest structures on Mt. Chortiatis (northern Greece)

EL proyecto estudia y analiza la estructura de cuatro bosques en el monte Chortiatis, Grecia.

Long-term natural acidification of upland sites in Cumbria: Evidence from post-glacial lake sediments

Studies by the Freshwater Biological Association over the last 25 years have supplied data relevant to the levels of acidity in local soils and water before the onset of industrial pollution and current interest in acid rain. This article reviews published analysis from cores of lake sediments, in or near the catchment of the River Duddon. Electron spin resonance spectra of humic acids and iodine values confirm evidence from pollen analysis for a history of progressive acidification of the source material of lake sediments since before 5000 radiocarbon years, in upland catchments of the Lake District. Processes involved included: removal of basic ions from soils by rainfall, the effects of which were intensified by removal by man of deciduous forest; acidification of soils and waters by decomposition products of Calluna and further acidification of waters by Sphagnum species which colonized habitats where drainage became impeded by paludification processes.