Selective Valorization of Bio-derived Levulinic Acid and Its Derivatives into Hydrocarbons and Biochemicals by Using Hydrosilylation.

Herein we report an efficient hydrosilylation strategy to selectively defunctionalize biomass-derived levulinic acid into value-added chemicals such as pentane-1,4-diol, pentan-2-ol, 2-MTHF and C5 hydrocarbons by using cost-effective silanes and the commercially available catalyst B(C6 F5 )3 at room temperature. All reactions work well in chlorinated solvents but, as a greener alternative, most reactions can be run in toluene or solvent-less.

Ru-Catalyzed Completely Deoxygenative Coupling of 2-Arylethanols through Base-Induced Net Decarbonylation.

Substituted arylethanols can be coupled by using a readily available Ru catalyst in a fully deoxygenative manner to produce hydrocarbon chains in one step. Control experiments indicate that the first deoxygenation occurs through an aldol condensation, whereas the second occurs through a base-induced net decarbonylation. This double deoxygenation enables further development in the use of alcohols as versatile and green alkylating reagents, as well as in other fields, such as deoxygenation and upgrading of overfunctionalized biomass to produce hydrocarbons.

Se-C Cleavage of Hexane Selenol at Steps on Au(111).

Selenols are considered as an alternative to thiols in self-assembled monolayers, but the Se-C bond is one limiting factor for their usefulness. In this study, we address the stability of the Se-C bond by a combined experimental and theoretical investigation of gas-phase-deposited hexane selenol (CH3(CH2)5SeH) on Au(111) using photoelectron spectroscopy, scanning tunneling microscopy, and density functional theory (DFT). Experimentally, we find that initial adsorption leaves atomic Se on the surface without any carbon left on the surface, whereas further adsorption generates a saturated selenolate layer. The Se 3d component from atomic Se appears at 0.85 eV lower binding energy than the selenolate-related component. DFT calculations show that the most stable structure of selenols on Au(111) is in the form of RSe-Au-SeR complexes adsorbed on the unreconstructed Au(111) surface. This is similar to thiols on Au(111). Calculated Se 3d core-level shifts between elemental Se and selenolate in this structure nicely reproduce the experimentally recorded shifts. Dissociation of RSeH and subsequent formation of RH are found to proceed with high barriers on defect-free Au(111) terraces, with the highest barrier for scissoring R-Se. However, at steps, these barriers are considerably lower, allowing for Se-C bond breaking and hexane desorption, leaving elemental Se at the surface. Hexane is formed by replacing the Se-C bond with a H-C bond by using the hydrogen liberated from the selenol to selenolate transformation.

Ru-Catalyzed Cross-Dehydrogenative Coupling between Primary Alcohols to Guerbet Alcohol Derivatives: with Relevance for Fragrance Synthesis.

A simple method has been developed for the cross dehydrogenative coupling between two different primary alcohols using readily available RuCl2(PPh3)3 as a precatalyst through the borrowing-hydrogen approach. The present methodology is applicable to a large variety of alcohol derivatives including long chain aliphatic alcohols and heteroaryl alcohols. In addition, the methodology was applied in a straightforward protocol to synthesize commercially available fragrances such as Rosaphen and Cyclamenaldehyde in good yields.

Naphthyl Thio- and Carba-xylopyranosides for Exploration of the Active Site of ß-1,4-Galactosyltransferase 7 (ß4GalT7).

Xyloside analogues with substitution of the endocyclic oxygen atom by sulfur or carbon were investigated as substrates for ß-1,4-galactosyltransferase 7 (ß4GalT7), a key enzyme in the biosynthesis of glycosaminoglycan chains. The analogues with an endocyclic sulfur atom proved to be excellent substrates for ß4GalT7, and were galactosylated approximately fifteen times more efficiently than the corresponding xyloside. The 5a-carba-ß-xylopyranoside in the d-configuration proved to be a good substrate for ß4GalT7, whereas the enantiomer in the l-configuration showed no activity. Further investigations by X-ray crystallography, NMR spectroscopy, and molecular modeling provided a rationale for the pronounced activity of the sulfur analogues. Favorable π-π interactions between the 2-naphthyl moiety and a tyrosine side chain of the enzyme were observed for the thio analogues, which open up for the design of efficient GAG primers and inhibitors.

Dehydrogenation of methanol on Cu2O(100) and (111).

Adsorption and desorption of methanol on the (111) and (100) surfaces of Cu2O have been studied using high-resolution photoelectron spectroscopy in the temperature range 120-620 K, in combination with density functional theory calculations and sum frequency generation spectroscopy. The bare (100) surface exhibits a (3,0; 1,1) reconstruction but restructures during the adsorption process into a Cu-dimer geometry stabilized by methoxy and hydrogen binding in Cu-bridge sites. During the restructuring process, oxygen atoms from the bulk that can host hydrogen appear on the surface. Heating transforms methoxy to formaldehyde, but further dehydrogenation is limited by the stability of the surface and the limited access to surface oxygen. The (√3 × âˆš3)R30°-reconstructed (111) surface is based on ordered surface oxygen and copper ions and vacancies, which offers a palette of adsorption and reaction sites. Already at 140 K, a mixed layer of methoxy, formaldehyde, and CHxOy is formed. Heating to room temperature leaves OCH and CHx. Thus both CH-bond breaking and CO-scission are active on this surface at low temperature. The higher ability to dehydrogenate methanol on (111) compared to (100) is explained by the multitude of adsorption sites and, in particular, the availability of surface oxygen.

The creation of the Chagos marine protected area: a fisheries perspective(☆).

From a fisheries perspective, the declaration of a 640,000 km² "no-take" Marine Protected Area (MPA) in the Chagos Archipelago in 2010 was preceded by inadequate consideration of the scientific rationale for protection. The entire area was already a highly regulated zone which had been subject to a well-managed fisheries licensing system. The island of Diego Garcia, the only area where there is evidence of overfishing has, because of its military base, been excluded from the MPA. The no-take mandate removes the primary source of sustenance and economic sustainability of any inhabitants, thus effectively preventing the return of the original residents who were removed for political reasons in the 1960s and 1970s. The principles of natural resource conservation and use have been further distorted by forcing offshore fishing effort to other less well-managed areas where it will have a greater negative impact on the well-being of the species that were claimed to be one of the primary beneficiaries of the declaration. A failure to engage stakeholders has resulted in challenges in both the English courts and before an international tribunal.

Diverging strategies to planning an ecologically coherent network of MPAs in the North Sea: the roles of advocacy, evidence and pragmatism in the face of uncertainty.

The North Sea is one of the most economically important seas in the world due to productive fisheries, extensive oil and gas fields, busy shipping routes, marine renewable energy development and recreational activity. Unsurprisingly, therefore, the use of marine protected areas (here defined widely to include fisheries closed areas and no-take marine reserves) in its management has generated considerable controversy-particularly with regards to the design of a regional ecologically coherent MPA network to meet international obligations. Drawing on three MPA processes currently occurring in the UK North Sea, we examine the real-world problems that make the designation of MPA networks challenging. The political problems include: disagreement among (and within) sectors over policy objectives and priorities, common access to fisheries resources at the EU level increasing the scale at which decisions have to be made and lack of an integrated strategy for implementing protected areas in the North Sea. The scientific problems include the patchy knowledge of benthic assemblages, limited knowledge of fishing gear-habitat interactions, and the increased risk of unforeseen externalities if human activity (predominantly fishing) is displaced from newly protected sites. Diverging stakeholder attitudes to these problems means that there is no consensus on what ecological coherence actually means. Ultimately, we caution against 'quick-fix' solutions that are based on advocacy and targets, as they create confusion and undermine trust in the planning process. We argue for a more pragmatic approach to marine protection that embraces the complexity of the social and political arena in which decisions are made.

Synthesis of an orthogonal topological analogue of helicene.

The synthesis of an orthogonal topological pentamer analogue of helicene is presented. This analogue forms a tubular structure with its aromatic systems directed parallel to the axis of propagation, which creates a cavity with the potential to function as a host molecule. The synthetic strategy reported, based on a series of repeating Friedländer condensations that utilize pyrido[3,2-d]pyrimidine moieties as protected amino aldehydes, allows for the facile access of higher generations of helical, tubular structures. As a result of the synthetic strategy, only a helical isomer of the pentamer is possible. The structure and absolute configuration of the pentamer were elucidated from a combination of NMR spectroscopic data, optical properties, X-ray structures, and by comparison of an experimental electronic circular dichroism spectrum to a calculated spectrum.

The reniform reflecting superposition compound eyes of Nephrops norvegicus: optics, susceptibility to light-induced damage, electrophysiology and a ray tracing model.

The large reniform eyes of the reptant, tube-dwelling decapod Nephrops norvegicus are described in detail. Optically these reflecting superposition compound eyes are a little unusual in that they are laterally flattened, a feature that may enhance their sensitivity in that region, albeit at the expense of resolution. Electrophysiological and anatomical investigations suggest that the eyes are tuned to appropriate spectral and temporal sensitivities in the long and short term through movement of proximal pigments and possibly rhabdom adaptation. Although exposure to ambient surface light intensities is shown to cause damage to the retinal layer, especially in deeper living animals, there is no evidence yet that demonstrates an impact of eye damage on their survival. It is suggested that experimentation on marine decapods, with sensitive eyes, requires that particular attention is paid to their light environment.

Nephrops fisheries in European waters.

This review focuses on the Norway lobster (Nephrops norvegicus) as a resource, describing how the fishery has developed from the 1960s to the present day to become one of the most economically important fisheries in Europe. In 2010, the total landings were 66,500 tonnes, of which UK fishers landed a significant part (58.1%). The Nephrops fishery is also important for countries such as Ireland (11.7% of the total) and Sweden (1.9%) where it is of regional importance. Some are also taken in the Mediterranean, where Italian, Spanish and Greek fishers together take approximately 7% of the total landing. More than 95% of Nephrops are taken using single- or multi-rig trawlers targeting Nephrops or in mixed species fisheries. In regions such as Western Scotland and the Swedish West Coast, creel fisheries account for up to a quarter of the total landings. Across the range, a small proportion (<5%) is taken using traps in a fishery characterised by larger sized animals that gain a higher price and have lower discard and by-catches of ground fish with low mortalities. The trawling sector, however, is reducing the by-catches of ground fish with the aid of technical measures, such as square-mesh panels and grids and national systems of incentives. Assessments for Nephrops are operated via the 34 functional units (FUs) regarded as stocks. Changes in management procedures have arisen as a result of the advisory input from underwater TV fishery-independent stock surveys. The total allowable catch does not follow FUs but is agreed upon per management area.

Ligand-Promoted [Pd]-Catalyzed α-Alkylation of Ketones through a Borrowing-Hydrogen Approach.

A new class of palladium complexes bearing bidentate 2-hydroxypyridine based ligands have been prepared and fully characterized. The applications of these new complexes towards ketone alkylation reactions with alcohols through a metal-ligand cooperative borrowing-hydrogen (BH) process were demonstrated.

DNA metabarcoding reveals the dietary profiles of a benthic marine crustacean, Nephrops norvegicus.

Norwegian lobster, Nephrops norvegicus, are a generalist scavenger and predator capable of short foraging excursions but can also suspension feed. Existing knowledge about their diet relies on a combination of methods including morphology-based stomach content analysis and stable isotopes, which often lack the resolution to distinguish prey items to species level particularly in species that thoroughly masticate their prey. DNA metabarcoding overcomes many of the challenges associated with traditional methods and it is an attractive approach to study the dietary profiles of animals. Here, we present the diet of the commercially valuable Nephrops norvegicus using DNA metabarcoding of gut contents. Despite difficulties associated with host amplification, our cytochrome oxidase I (COI) molecular assay successfully achieves higher resolution information than traditional approaches. We detected taxa that were likely consumed during different feeding strategies. Dinoflagellata, Chlorophyta and Bacillariophyta accounted for almost 50% of the prey items consumed, and are associated with suspension feeding, while fish with high fisheries discard rates were detected which are linked to active foraging. In addition, we were able to characterise biodiversity patterns by considering Nephrops as natural samplers, as well as detecting parasitic dinoflagellates (e.g., Hematodinium sp.), which are known to influence burrow related behaviour in infected individuals in over 50% of the samples. The metabarcoding data presented here greatly enhances a better understanding of a species' ecological role and could be applied as a routine procedure in future studies for proper consideration in the management and decision-making of fisheries.

Palladium(II)-catalyzed oxidative cyclization of allylic tosylcarbamates: scope, derivatization, and mechanistic aspects.

A highly selective oxidative palladium(II)-catalyzed (Wacker-type) cyclization of readily available allylic tosylcarbamates is reported. This operationally simple catalytic reaction furnishes tosyl-protected vinyl-oxazolidinones, common precursors to syn-1,2-amino alcohols, in high yield and excellent diasteroselectivity (>20:1). It is demonstrated that both stoichiometric amounts of benzoquinone (BQ) as well as aerobic reoxidation (molecular oxygen) is suitable for this transformation. The title reaction is shown to proceed through overall trans-amidopalladation of the olefin followed by ß-hydride elimination. This process is scalable and the products are suitable for a range of subsequent transformations such as: kinetic resolution (KR) and oxidative Heck-, Wacker-, and metathesis reactions.

A mononuclear iron(III) complex with unusual changes of color and magneto-structural properties with temperature: synthesis, structure, magnetization, multi-frequency ESR and DFT study.

From the reaction of 2-hydroxy-6-methylpyridine (L) with iron(II) tetrafluoroborate, a new mononuclear iron(III) octahedral complex [FeL6](BF4)3 has been isolated. The color of the complex reversibly changed from red at room temperature to yellow-orange at the liquid nitrogen temperature. Magnetization measurements indicate that iron(III) in [FeL6](BF4)3 is in a high-spin state S = 5/2, from room temperature to 1.8 K. The high-spin ground state of iron(III) is also confirmed by DFT calculations. Although the spin-crossover of the complex is not observed, X-band and multifrequency high-field/high-frequency electron spin resonance (ESR) spectroscopy shows rather uncommon iron(III) spectra at room temperature and an unusual change with cooling. Spectral simulations reveal that the S = 5/2 ground state multiplet of the complex can be characterized by the temperature independent axial zero-field splitting parameter of |D| = +2 GHz (0.067 cm-1) while the value of the rhombic parameter E of the order of some tenths MHz increases on lowering the temperature. Single crystal X-ray diffraction (SCXRD) shows that the iron(III) coordination geometry does not change with temperature while supramolecular interactions are temperature dependent, influencing the iron(III) rhombicity. Additionally, the DFT calculations show temperature variation of the HOMO-LUMO gap, in agreement with the changes of color and ESR-spectra of the iron(III) complex with temperature.

Can a key boreal Calanus copepod species now complete its life-cycle in the Arctic? Evidence and implications for Arctic food-webs.

The changing Arctic environment is affecting zooplankton that support its abundant wildlife. We examined how these changes are influencing a key zooplankton species, Calanus finmarchicus, principally found in the North Atlantic but expatriated to the Arctic. Close to the ice-edge in the Fram Strait, we identified areas that, since the 1980s, are increasingly favourable to C. finmarchicus. Field-sampling revealed part of the population there to be capable of amassing enough reserves to overwinter. Early developmental stages were also present in early summer, suggesting successful local recruitment. This extension to suitable C. finmarchicus habitat is most likely facilitated by the long-term retreat of the ice-edge, allowing phytoplankton to bloom earlier and for longer and through higher temperatures increasing copepod developmental rates. The increased capacity for this species to complete its life-cycle and prosper in the Fram Strait can change community structure, with large consequences to regional food-webs.

Bis(1,3-dimesitylimidazol-yl)gold(I) 2,4,8,10-tetra-phenyl-1,3,5,7,9,11-hexa-oxa-2,4,8,10-tetra-bora-6-borataspiro-[5.5]undeca-ne.

The Au(I) atom in the title compound, [Au(C(21)H(24)N(2))(2)](C(24)H(20)B(5)O(6)), adopts a slightly distorted linear AuC(2) coordination geometry arising from its coordination by two mesitylenic N-heterocyclic carbene ligands, forming an overall cationic complex. The dihedral angle between the imidazole rings is 57.3 (6)°. In the crystal, the components are linked by weak C-H⋯O hydrogen bonds.

Molecular structure upon compression and stability toward oxidation of Langmuir films of unsaturated fatty acids: a vibrational sum frequency spectroscopy study.

Vibrational sum frequency spectroscopy (VSFS) has been used to determine the stability toward oxidation in air of a series of unsaturated fatty acids, measuring as a function of time the changes in the chemical structure and conformational order of films spread on a Langmuir trough. The fatty acids studied consisted of a 20-carbon backbone with increasing numbers of cis double bonds in the chain: 11c-eicosenoic acid (20:1 EA, omega-9), 11c,14c-eicosadienoic acid (20:2 EA, omega-6), and 11c,14c,17c-eicosatrienoic acid (20:3 EA, omega-3). Measurements at constant surface pressure show that double bonds are lost from the surface region and that drops in intensity of the vinyl CH stretch are detectable within a few minutes of spreading the monolayer. The results are consistent with the fatty acid peroxidation free radical mechanism. The sum frequency spectra also reveal that what remains on the surface is conformationally more disordered with a larger number of gauche defects. The oxidation kinetics are found to be strongly dependent on the packing density of the monolayer, being more stable at higher pressures. Oxidation can be avoided by purging the system in an inert atmosphere. Finally, the molecular structure upon compression was tracked in unoxidized monolayers. The results suggest that the packing and orientation of the double bond sections of all three unsaturated fatty acids show remarkable similarities, with the direction of the double bonds approximately parallel to each other irrespective of the number of unsaturations in the chain, with the 20:3 EA probably forming "iron-angle" structures. The possibility of unsaturated chains in a "hairpin" configuration is discarded for area per molecules smaller than approximately 50 A(2), which corresponds to the lowest surface pressure measured with VSFS.

Laboratory-based observations of behaviour in Northern krill (Meganyctiphanes norvegica Sars).

The behaviour of planktonic animals remains poorly understood due to the difficulty of observing them in situ without influencing their behaviour. Here we review experiments on the behavioural responses of Northern krill, Meganyctiphanes norvegica (and related organisms), in isolation in laboratory-based aquaria. The value of this approach lies in the close observation that is possible; the downside is the uncertainty as to how well the observed behaviour relates to the natural behaviour of the subject animal. We discuss studies of swimming and swarming, and the responses of krill to light. We consider techniques involving automatic recordings that avoid, to some extent, making subjective decisions on behaviour. The effects of isolation of such a gregarious animal and of exposure to unnaturally high light levels are also considered. We conclude that such experiments can be of great value as long as these limiting factors are addressed.

[2,6-Bis(di-tert-butyl-phosphinometh-yl)phenyl-κP,C,P'](trifluoro-acetato)palladium(II).

The Pd(II) atom in the title compound, [Pd(C(2)F(3)O(2))(C(24)H(43)P(2))], adopts a distorted square-planar geometry with the P atoms in a trans arrangement, forming two five-membered chelate rings. Four intra-molecular C-H⋯O hydrogen bonds occur. The crystal packing reveals one weak inter-molecular C-H⋯O hydrogen bond, which self-assembles the mol-ecules into infinite chains parallel to the b axis.