Reversing “Empty Forest Syndrome” in Southeast Asia

[Extract] The diverse tropical forests of Southeast Asia are home to some of the most mysterious and beautiful wildlife species in the world, some of which have only been discovered in the last few decades. Home to species such as the antelope-like Saola (the Asian “unicorn”), which was only discovered in 1992 and that no biologist has seen in the wild, capturing the imagination of scientists, reporters and the public alike. Home to an extensive community of animals small and large, from civets to muntjacs, striped rabbits to Doucs, porcupines to pigs, tortoises to wild cattle. However, Southeast Asia also holds a higher proportion of globally threatened vascular plant, reptile, bird and mammal species than any other region on the planet. Today, these irreplaceable forests are often harboring the ghosts of these amazing species, victims of a barbaric and widespread hunting technique—the use of homemade and cheap wire snares that catch animals, leaving them trapped, often to suffer for days, before death. This hunting technique makes no distinction between common and Endangered species and is indiscriminately laying waste to any wildlife species regardless of their size and shape: Saola, Grey-shanked Douc, Southeast Asian Porcupine, Sambar Deer, Marbled Cat, Hog Badger, and the list goes on and on. Imagine walking into the Adirondacks in the northeastern United States and not seeing a single squirrel or raccoon. This idea appropriately has an ominous name: “empty forest syndrome.

Advances in precision medicine: tailoring individualised therapies

The traditional bench-to-bedside pipeline involves using model systems and patient samples to provide insights into pathways deregulated in cancer. This discovery reveals new biomarkers and therapeutic targets, ultimately stratifying patients and informing cohort-based treatment options. Precision medicine (molecular profiling of individual tumors combined with established clinical-pathological parameters) reveals, in real-time, individual patient's diagnostic and prognostic risk profile, informing tailored and tumor-specific treatment plans. Here we discuss advances in precision medicine presented at the Irish Association for Cancer Research Annual Meeting, highlighting examples where personalized medicine approaches have led to precision discovery in individual tumors, informing customized treatment programs

DFT Studies of Au(I) Catalysed Reactions : Anion Effects and Reaction Selectivity

Density functional theory (DFT) is a powerful tool that can aid in the exploration and development of synthetic chemistry, and its use is often applied in the chemistry of gold(I) catalysis. In this review, we discuss two different facets of these calculations – namely, the exploration and explanation of anion effects, and the regioselectivity and speciation of gold(I)-catalysed reactions. The research described herein clearly shows the importance of including the anion in DFT studies of Au(I)-catalysed reactions, especially when using low polarity solvents, or where hydrogen-bonding is prevalent. Additionally, we show that whilst using DFT to study the selectivity of reactions can be successful, benchmarking the computational results against experimental data is vitally important for ensuring that the model is accurately describing the observed results

"Back-to-Front" Indole Synthesis using Silver(I) Catalysis : Unexpected C-3 Pyrrole Activation Mode Supported by DFT

An efficient silver(I)-catalyzed method is reported for the synthesis of substituted indoles, most notably 5-hydroxy-derivatives, via π-acidic alkyne activation. Most methods for the preparation of indoles involve annulation of a benzene precursor, but the method reported herein is unusual in that pyrrole precursors are used. Density Functional Theory (DFT) studies suggest that these reactions proceed via initial activation of the pyrrole C-3 position before undergoing subsequent rearrangement, contradicting the conventional wisdom that pyrroles are more nucleophilic through C-2

Ring expansion reactions of P=O-containing molecules

A series of ring expansion reactions of P=O-containing molecules have been developed for the synthesis of medium-sized ring cyclic phosphonate esters and phosphonamidates. The reactivity trends initially appear to be counter-intuitive, compared with more well established ring expansion reactions of lactam derivatives, but are explained by considering the differences in heteroatom bonding to P and C respectively

Synthesis of macrocyclic and medium-sized ring thiolactones via the ring expansion of lactams

A side chain insertion method for the ring expansion of lactams into macrocyclic thiolactones is reported, that can also be incorporated into Successive Ring Expansion (SuRE) sequences. The reactions are less thermodynamically favourable than the analogous lactam- and lactone-forming ring expansion processes (with this notion supported by DFT data), but nonetheless, three complementary protecting group strategies have been developed to enable this challenging transformation to be achieved

Questioning the rise of gelatinous zooplankton in the World's oceans

During the past several decades, high numbers of gelatinous zooplankton species have been reported in many estuarine and coastal ecosystems. Coupled with media-driven public perception, a paradigm has evolved in which the global ocean ecosystems are thought to be heading toward being dominated by “nuisance” jellyfish. We question this current paradigm by presenting a broad overview of gelatinous zooplankton in a historicalcontext to develop the hypothesis that population changes reflect the human-mediated alteration of global ocean ecosystems. To this end, we synthesize information related to the evolutionary context of contemporary gelatinous zooplankton blooms, the human frame of reference forchanges in gelatinous zooplankton populations, and whether sufficient data are available to have established the paradigm. We conclude that the current paradigm in which it is believed that there has been a global increase in gelatinous zooplankton is unsubstantiated, and we develop a strategy for addressing the critical questions about long-term, human-related changes in the sea as they relate to gelatinous zooplankton blooms

Silver–N-heterocyclic carbenes in π–Activation: Synergistic effects between the ligand ring size and the anion

A series of 12 silver­(I)–N-heterocyclic carbene (NHC) complexes were prepared featuring five- (both saturated and unsaturated backbone), six-, and seven-membered ring ligand scaffolds. The N-substituents of the NHCs were diisopropylphenyl in all cases, while the anion was varied between bromide, acetate, and triflate. The complexes were evaluated as catalysts in the spirocyclization of 1-(1H-indol-3-yl)-4-phenylbut-3-yn-2-one to give a spirocyclic indolenine product. To our knowledge, it is the first time that a systematic study has been conducted to examine the effects of both NHC ring size and anion in this type of silver-catalyzed reaction. While the acetate and triflate complexes catalyzed the reaction to 100% conversion, the bromide complexes exhibited a significant ligand/anion effect. Reactions catalyzed by both complexes bearing the five-membered ring NHC ligands and the complex bearing the seven-membered ring NHC ligand stalled after approximately two turnovers. However, the bromide complex bearing the six-membered ring NHC ligand catalyzes the reaction to almost full conversion, similarly to the acetate and triflate complexes. This demonstrates that the NHC ligand ring size can have a dramatic effect in these types of reactions and does not necessarily display a linear correlation