Amine-free approach toward N-toluenesulfonyl amidine construction: a phosphite-mediated Beckmann-like coupling of oximes and p-toluenesulfonyl azide.

Atom hopping: A chlorophosphite-mediated Beckmann ligation of oximes and p-toluenesulfonyl azide gives access to N-sulfonyl phosphoramidines in good to excellent yields. The reaction proceeds under exceptionally mild conditions and constitutes a bioorthogonal approach toward amidines by avoiding the use of amines and transition-metal catalysts. dmp-ol=3,3-dimethylpropanediol.

Direct acyl substitution of carboxylic acids: a chemoselective O- to N-acyl migration in the traceless Staudinger ligation.

A chlorophosphite-modified, Staudinger-like acylation of azides involving a highly chemoselective, direct nucleophilic acyl substitution of carboxylic acids is described. The reaction provides the corresponding amides with analytical purity in 32-97% yield after a simple aqueous workup without the need for a pre-activation step. The use of chlorophosphites as dual carboxylic acid-azide activating agents enables the formation of acyl C-N bonds in the presence of a wide range of nucleophilic and electrophilic functional groups, including amines, alcohols, amides, aldehydes, and ketones. The coupling of carboxylic acids and azides for the formation of alkyl amides, sulfonyl amides, lactams, and dipeptides is described.

Scavenging: how carnivores and carrion structure communities.

Recent advances in the ecology of food webs underscore the importance of detritus and indirect predator-prey effects. However, most research considers detritus as an invariable pool and predation as the only interaction between carnivores and prey. Carrion consumption, scavenging, is a type of detrital feeding that should have widespread consequences for the structure and stability of food webs. Providing access to high-quality resources, facultative scavenging is a ubiquitous and phylogenetically widespread strategy. In this review, we argue that scavenging is underestimated by 16-fold in food-web research, producing inflated predation rates and underestimated indirect effects. Furthermore, more energy is generally transferred per link via scavenging than predation. Thus, future food-web research should consider scavenging, especially in light of how major global changes can affect scavengers.

Pollen foraging behaviour of solitary Hawaiian bees revealed through molecular pollen analysis.

Obtaining quantitative information concerning pollinator behaviour has become a primary objective of pollination studies, but methodological limitations hinder progress towards this goal. Here, we use molecular genetic methods in an ecological context to demonstrate that endemic Hawaiian Hylaeus bees (Hymenoptera: Colletidae) selectively collect pollen from native plant species in Haleakala and Hawaii Volcanoes National Parks. We identified pollen DNA from the crops (internal storage organs) of 21 Hylaeus specimens stored in ethanol for up to 3 years. Genetic analyses reveal high fidelity in pollen foraging despite the availability of pollen from multiple plant species present at each study site. At high elevations in Haleakala, pollen was available from more than 12 species of flowering plants, but Hawaiian silversword (Argyroxiphium sandwicense subsp. macrocephalum) comprised 86% of all pollen samples removed from bee crops. At lower elevations in both parks, we only detected pukiawe (Leptecophylla (Styphelia) tameiameiae) pollen in Hylaeus crops despite the presence of other plant species in flower during our study. Furthermore, 100% of Hylaeus crops from which we successfully identified pollen contained native plant pollen. The molecular approaches developed in this study provide species-level information about floral visitation of Hawaiian Hylaeus that does not require specialized palynological expertise needed for high-throughput visual pollen identification. Building upon this approach, future studies can thus develop appropriate and customized criteria for assessing mixed pollen loads from a broader range of sources and from other global regions.

Predation or scavenging? Thoracic muscle pH and rates of water loss reveal cause of death in arthropods.

The difficulty of directly observing predatory events hinders a complete understanding of how predation structures food webs. Indirect approaches such as PCR-based and isotopic analyses clarify patterns of resource consumption but fail to distinguish predation from scavenging. Given that facultative scavenging is a ubiquitous and phylogenetically widespread foraging strategy, an improved ability to discriminate prey from carrion is needed to enhance an understanding of the demographic effects of consumption and the true nature of trophic interactions. Using physiological properties of muscle tissue - specifically pH and rate of water loss - we develop a novel method to discriminate prey from carrion collected by scavenging hymenopteran predators. Our focal system is the western yellowjacket (Vespula pensylvanica), a common scavenging predator in Hawaii and western North America. Prior to consumption, the physical properties of hymenopteran muscle tissue change in a quantifiable and deterministic manner post mortem and can be used to estimate the time and putative cause of death of diet items. Applying this method in laboratory and field situations resulted in the correct identification of prey and carrion in 49 out of 56 cases (88%). Although further investigation is needed to determine how post-mortem physiology of diet items changes in the guts of consumers, the approaches developed in this study can be used to distinguish predation from scavenging by central-place foragers (particularly arthropods). Such information will provide a more definitive characterization of species interactions and food webs.

Life history plasticity magnifies the ecological effects of a social wasp invasion.

An unresolved question in ecology concerns why the ecological effects of invasions vary in magnitude. Many introduced species fail to interact strongly with the recipient biota, whereas others profoundly disrupt the ecosystems they invade through predation, competition, and other mechanisms. In the context of ecological impacts, research on biological invasions seldom considers phenotypic or microevolutionary changes that occur following introduction. Here, we show how plasticity in key life history traits (colony size and longevity), together with omnivory, magnifies the predatory impacts of an invasive social wasp (Vespula pensylvanica) on a largely endemic arthropod fauna in Hawaii. Using a combination of molecular, experimental, and behavioral approaches, we demonstrate (i) that yellowjackets consume an astonishing diversity of arthropod resources and depress prey populations in invaded Hawaiian ecosystems and (ii) that their impact as predators in this region increases when they shift from small annual colonies to large perennial colonies. Such trait plasticity may influence invasion success and the degree of disruption that invaded ecosystems experience. Moreover, postintroduction phenotypic changes may help invaders to compensate for reductions in adaptive potential resulting from founder events and small population sizes. The dynamic nature of biological invasions necessitates a more quantitative understanding of how postintroduction changes in invader traits affect invasion processes.

Three structural roles for water in bone observed by solid-state NMR.

Hydrogen-bearing species in the bone mineral environment were investigated using solid-state NMR spectroscopy of powdered bone, deproteinated bone, and B-type carbonated apatite. Using magic-angle spinning and cross-polarization techniques three types of structurally-bound water were observed in these materials. Two of these water types occupy vacancies within the apatitic mineral crystal in synthetic carbonated apatite and deproteinated bone and serve to stabilize these defect-containing crystals. The third water was observed at the mineral surface in unmodified bone but not in deproteinated bone, suggesting a role for this water in mediating mineral-organic matrix interactions. Direct evidence of monohydrogen phosphate in a (1)H NMR spectrum of unmodified bone is presented for the first time. We obtained clear evidence for the presence of hydroxide ion in deproteinated bone by (1)H MAS NMR. A (1)H-(31)P heteronuclear correlation experiment provided unambiguous evidence for hydroxide ion in unmodified bone as well. Hydroxide ion in both unmodified and deproteinated bone mineral was found to participate in hydrogen bonding with neighboring water molecules and ions. In unmodified bone mineral hydroxide ion was found, through a (1)H-(31)P heteronuclear correlation experiment, to be confined to a small portion of the mineral crystal, probably the internal portion.

Highly ordered interstitial water observed in bone by nuclear magnetic resonance.

UNLABELLED: NMR was used to study the nanostructure of bone tissue. Distance measurements show that the first water layer at the surface of the mineral in cortical bone is structured. This water may serve to couple the mineral to the organic matrix and may play a role in deformation. INTRODUCTION: The unique mechanical characteristics of bone tissue have not yet been satisfactorily connected to the exact molecular architecture of this complex composite material. Recently developed solid-state nuclear magnetic resonance (NMR) techniques are applied here to the mineral component to provide new structural distance constraints at the subnanometer scale. MATERIALS AND METHODS: NMR dipolar couplings between structural protons (OH(-) and H(2)O) and phosphorus (PO(4)) or carbon (CO(3)) were measured using the 2D Lee-Goldburg Cross-Polarization under Magic-Angle Spinning (2D LG-CPMAS) pulse sequence, which simultaneously suppresses the much stronger proton-proton dipolar interactions. The NMR dipolar couplings measured provide accurate distances between atoms, e.g., OH and PO(4) in apatites. Excised and powdered femoral cortical bone was used for these experiments. Synthetic carbonate ( approximately 2-4 wt%)-substituted hydroxyapatite was also studied for structural comparison. RESULTS: In synthetic apatite, the hydroxide ions are strongly hydrogen bonded to adjacent carbonate or phosphate ions, with hydrogen bond (O-H) distances of approximately 1.96 A observed. The bone tissue sample, in contrast, shows little evidence of ordered hydroxide. Instead, a very ordered (structural) layer of water molecules is identified, which hydrates the small bioapatite crystallites through very close arrangements. Water protons are approximately 2.3-2.55 A from surface phosphorus atoms. CONCLUSIONS: In synthetic carbonated apatite, strong hydrogen bonds were observed between the hydroxide ions and structural phosphate and carbonate units in the apatite crystal lattice. These hydrogen bonding interactions may contribute to the long-range stability of this mineral structure. The biological apatite in cortical bone tissue shows evidence of hydrogen bonding with an ordered surface water layer at the faces of the mineral particles. This structural water layer has been inferred, but direct spectroscopic evidence of this interstitial water is given here. An ordered structural water layer sandwiched between the mineral and the organic collagen fibers may affect the biomechanical properties of this complex composite material.

Synthesis of a digermane-containing tricylic nonadecadienedione incorporating an equivalent of ring-opened THF.

The combination of 2 equiv of bis[bis(trimethylsilyl)amide]germylene (5) with 2 equiv of 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD) in tetrahydrofuran (THF) results in the ring-opening of 1 equiv of THF to form 2,2,8,8-tetrakis(1,1,1,3,3,3-hexamethyl-disilazan-2-yl)-5,16-diphenyl-7,9,14-trioxa-1,3,5,16,18,19-hexaaza-2,8-digerma-tricyclo[13.2.1.13,6]nonadeca-6(19),15(18)-diene-4,17-dione (6). This fast and nearly quantitative reaction builds a 15-membered ring from five different molecules. The new ring, structurally assigned by X-ray crystallography, contains a flexible methylene chain that moves rapidly on the NMR time scale.

Comparison of "polynaphthalenes" prepared by two mechanistically distinct routes.

The Bergman cyclization has long been known to produce polymers as side products. More recently, this attribute has been harnessed for the production of conjugated materials. However, the structures of these polymers have not been established. To resolve this question, the metal-catalyzed polymerization of 1,4-dibromonaphthalene and thermal polymerization of o-diethynylbenzene were conducted. Two distinct polymers were obtained. Comparison of IR spectroscopy, MALDI-TOF MS, solid-state NMR spectroscopy, UV-vis reflectance spectroscopy, and pyrolysis GC-MS data indicates that only one of the polymers is consistent with poly(1,4-naphthalene).

Determination of the conformation and stability of simple homopolypeptides using solid-state NMR.

15N CPMAS, 13C CPMAS and 1H CRAMPS spectra of several polypeptide samples were compared to determine the useful features of each technique. 13C CPMAS is the most well-established technique and is useful for quick determination of secondary structure. The 15N nucleus is more sensitive to exact hydrogen-bonding parameters, which complicates interpretation of the spectra. However, it is better for resolving end effects and structural types in short oligomers. 1H CRAMPS spectra are similar to 13C CPMAS in the information obtained, but the resolution is not as good. Using 13C CPMAS, the conformation of polyglycine was investigated in detail. Precipitation from solvents such as DCA or TFA resulted in the rippled beta-sheet structure (PG I), while 3(1)-helix (PG II) was formed by precipitation from aqueous solutions of LiBr. Grinding the sample resulted in an increase in the amount of PG I, indicating that this form is more stable in the solid state. These results agree with previous work on poly(L-alanine) showing that the beta-sheet form is more stable in the solid state. Homopolypeptides with larger side chains did not change conformation upon grinding due to the greater difficulty in disrupting van der Waals interactions and inertia of the large side chains.