Species of two paleoendemic sap beetle genera of the Tribe Nitidulini (Nitidulidae: Coleoptera) from the Baltic and Dominican amber

Omositoidea gigantea Schaufuss, 1892 is redescribed; O. pubescens sp. nov. from the Baltic amber, Palaeometopia dominicana gen. et sp. nov. and P. colorata gen. et sp. nov. from the Dominican amber are described. The taxonomic position of the two genera and their probable bionomy are discussed.     

On the find of adult Micromalthus (Coleoptera, Micromalthidae) in Dominican amber

An adult of Micromalthus is discovered in amber for the first time. The species, from the Miocene Dominican amber, is described as M. anansi sp. nov., and is generally similar to Recent M. debilis, but differs in the longer legs and antennae. The Miocene species appears to be less fetalized than its modern counterpart.     

Deuterium isotope effects in carbohydrates revisited. Cryoprobe studies of the anomerization and NH to ND deuterium isotope induced 13C NMR chemical shifts of acetamidodeoxy and aminodeoxy sugars

Complete ¹H and ¹³C NMR chemical shift assignments have been generated from a series of acetamidodeoxy and aminodeoxy sugar derivatives. For free sugars, the enhanced sensitivity of an NMR cryoprobe allowed simple 1D and 2D NMR spectra to be obtained from essentially single anomers, before significant mutarotation had occurred. The NMR assignments have been used to characterize deuterium isotope effects on ¹³C chemical shifts measured under conditions of slow NH to ND exchange in single solutions. Within a range of 0 to −0.138 ppm, β, γ, δ, and ζ deuterium isotope effects have been observed, thus providing additional reference data for assignment of the ¹³C NMR spectra of nitrogenous saccharides.     

A fossil scorpion Tityus geratus new species (Scorpiones: Buthidae) from Dominican Amber

A fossil scorpion, Tityus geratus (Scorpioncs: Buthidae) n. sp., is described from Dominican amber. This is the third described amber Tityus sp. and the third Dominican amber scorpion. On the basis of the amber finds and available knowledge on the present distribution of Tityus spp. in the Antilles, the vicariance model of Caribbean biogeography can be evoked to best explain the present distribution of this genus.     

A novel Ca2+-signal transduction inhibitor,kujigamberol C,isolated from Kuji amber

ABSTRACT

A novel labdane type diterpenoid, 15-nor-8-labden-13-ol, named kujigamberol C, was isolated from Kuji amber using a modified isolation method to increase the yield of biologically active compounds. The structure was determined using HREIMS, 1D and 2D NMR. Kujigamberol C showed growth-restoring activity against mutant yeast via Ca²⁺-signal transduction.     

Insect outbreaks produce distinctive carbon isotope signatures in defensive resins and fossiliferous ambers

Despite centuries of research addressing amber and its various inclusions, relatively little is known about the specific events having stimulated the production of geologically relevant volumes of plant resin, ultimately yielding amber deposits. Although numerous hypotheses have invoked the role of insects, to date these have proven difficult to test. Here, we use the current mountain pine beetle outbreak in western Canada as an analogy for the effects of infestation on the stable isotopic composition of carbon in resins. We show that infestation results in a rapid (approx. 1 year) (13)C enrichment of fresh lodgepole pine resins, in a pattern directly comparable with that observed in resins collected from uninfested trees subjected to water stress. Furthermore, resin isotopic values are shown to track both the progression of infestation and instances of recovery. These findings can be extended to fossil resins, including Miocene amber from the Dominican Republic and Late Cretaceous New Jersey amber, revealing similar carbon-isotopic patterns between visually clean ambers and those associated with the attack of wood-boring insects. Plant exudate δ(13)C values constitute a sensitive monitor of ecological stress in both modern and ancient forest ecosystems, and provide considerable insight concerning the genesis of amber in the geological record.     

3-Methoxyflavones and coumarins from Artemisia incanescens

Seven 3-methoxyflavones and three coumarins have been isolated from aerial parts of Artemisia incanescens. Their ¹H NMR spectra in DMSO-d₆ and CDCl₃ are compared and discussed. The hitherto unreported ¹³C NMR spectra of some of these compounds are also discussed.     

13C NMR spectroscopy of Pyrrolizidine alkaloids

The ¹³C NMR spectra of nine pyrrolizidine alkaloids of the macrocyclic diester type, seven of the corresponding N-oxides and of the parent base retronecine have been recorded and the signals assigned. The 13C NMR signals were found to be sensitive to structural variation in both the diester moiety and the heterocyclic ring system, providing useful information for structural elucidation, particularly when the ¹H NMR spectra may be difficult to interpret.     

Oriciopsin,a new ring-D cleaved tetranortriterpenoid,and flindersiamine from Oriciopsis glaberrima

A novel ring-D cleaved tetranortriterpenoid, oriciopsin and flindersiamine have been isolated from the whole plant extracts of Oriciopsis glaberrima. The structure of the new limonoid was determined from its ¹H NMR and ¹³C NMR spectra and by mass spectrometry.     

A walking stick,Clonistria dominicana n. sp. (Phasmatodea: Diapheromeridae) in Dominican amber

A walking stick, Clonistria dominicana n. sp. (Phasmatodea: Diapheromeridae: Diapheromerinae: Diapheromerini) is described from Dominican amber. The new species can be distinguished from extant members of the genus by the long hind leg tarsomere II (over six times the length of the foreleg tarsomere II), the short metanotum, which is only half the length of the median segment and the prominent median carina. Two phasmatid eggs in separate pieces of Dominican amber are also presented. One of these has characteristics of the genus Clonistria Stål, 1875, which supports the generic placement of C. dominicana. The second egg resembles those of the genus Malacomorpha Rehn, 1906 (Pseudophasmatidae: Pseudophasmatinae). Both of these genera occur in Hispaniola today.     

Paleotrichius dominicanus n. gen., n. sp. (Coleoptera; Cetoniidae), a flower beetle in Dominican amber

A new genus and species of flower beetle, Paleotrichius dominicanus, n. gen., n. sp. (Coleoptera: Cetoniidae: Trichinae) is described from Dominican amber. The new taxon is distinguished from all other New World trichines by the combination of the shape of the clypeus, pronotum, protibia, the femoral and tibial armature, the mesosternal process separating the middle coxae, the distinct strial pattern on the elytra and the approximate claws. The beetle may have been quite colourful and a strong flyer attracted to flowers. The larvae most likely developed in decaying hardwoods in the Dominican amber forest. This is the first amber representative of the family Cetoniidae.     

Fungal macrolides: Structure determination and biosynthesis of achaetolide,a lactone from Achaetomium cristalliferum

The structure of a new ten-membered lactone, achaetolide, isolated from cultures of Achaetomium cristalliferum is deduced from its mass and NMR spectra and from the study ofsomederivatives. The ¹³C NMR spectra of achaetolide enriched with [1-¹³C], [2-¹³C] and [1, 2-¹³C] acetate established its formation from eight intact acetate units via a precursor octaketide chain.     

Innovations in Generation and Analysis of 2D [C,H] COSY NMR Spectra for Metabolic Flux Analysis Purposes

2D [¹³C,¹H] COSY NMR is used by the metabolic engineering community for determining ¹³C–¹³C connectivities in intracellular compounds that contain information regarding the steady-state fluxes in cellular metabolism. This paper proposes innovations in the generation and analysis of these specific NMR spectra. These include a computer tool that allows accurate determination of the relative peak areas and their complete covariance matrices even in very complex spectra. Additionally, a method is introduced for correcting the results for isotopic non-steady-state conditions. The proposed methods were applied to measured 2D [¹³C,¹H] COSY NMR spectra. Peak intensities in a one-dimensional section of the spectrum are frequently not representative for relative peak volumes in the two-dimensional spectrum. It is shown that for some spectra a significant amount of additional information can be gained from long-range ¹³C–¹³C scalar couplings in 2D [¹³C,¹H] COSY NMR spectra. Finally, the NMR resolution enhancement by dissolving amino acid derivatives in a nonpolar solvent is demonstrated.     

Structural analysis and properties of dextran produced by Leuconostoc mesenteroides NRRL B-640

A water-soluble dextran was produced by purified dextransucrase from Leuconostoc mesenteroides NRRL B-640. The dextran was purified by alcohol precipitation. The structure of dextran was determined by FT-IR, ¹H NMR, ¹³C NMR and 2-dimensional NMR spectroscopic techniques. NMR techniques (1D ¹H, ¹³C and 2D HMQC) were used to fully assign the ¹H and ¹³C spectra. All the spectral data showed that the dextran contains d-glucose residues in a linear chain with consecutive α(1 → 6) linkages. No branching was observed in the dextran structure. The viscosity of dextran solution decreased with the increase in shear rate exhibiting a typical non-Newtonian pseudoplastic behavior. The surface morphology of dried and powdered dextran studied using Scanning electron microscopy revealed the cubical porous structure.     

How long can insect species exist? Evidence from extant and fossil Micromalthus beetles (Insecta: Coleoptera)

Six new fossils of Micromalthus (Coleoptera: Archostemata) from Dominican amber are compared with extant and previously described fossil micromalthid beetles. The amber inclusions are well preserved and all important morphological features are visible. Taking into account the morphological variability of the extant species Micromalthus debilis LeConte, 1878 , it is not possible to find any morphological features that distinguish the fossils from the extant species. This also applies to the Dominican amber inclusion described as Micromalthus anasi Perkovsky, 2008, which therefore is considered a junior synonym of M. debilis. The lack of morphological change in M. debilis over time might possibly be explained by unusually stable environmental conditions, as this species occupies a very specialized ecological niche in decaying timber. A general survey of fossil insects indistinguishable from extant species is presented. © 2009 The Linnean Society of London, Zoological Journal of the Linnean Society, 2010, 158 , 300–311.     

Bicalcasura maculata n. gen., n. sp. (Curculionoidea: Dryophthoridae) with a list of weevils described from Dominican amber

A new genus and species, Bicalcasura maculata n. gen., n. sp. (Coleoptera: Curculionoidea: Rhynchophorinae: Dryophthoridae) is described from Dominican amber as the first fossil member of the Tribe Diocalandrini. The new genus is characterised by procoxae located in the middle of the prothorax; a thick, short and strongly curved rostrum with the scape not reaching the pronotum; a weak extension of the rostrum in respect to the antennal attachment; slightly elongated fifth ventrite; narrow (not bilobed) third tarsomere and a pair of apical spurs on the protibiae. This set of characters separates the fossil from the extant genus Diocalandra Faust, 1894, the only other member of this tribe. A list of weevils (Curculionoidea) described from Dominican amber is included.

http://www.zoobank.org/urn:lsid:zoobank.org:pub:D25F7915-3C49-4E22-A37C-F574F573C67D     

Rollinicin and isorollinicin,cytotoxic acetogenins from Rollinia papilionella

Rollinicin and isorollinicin, two new linear acetogenins bearing bistetrahydrofuran moieties and an α,β-unsaturated-γ-lactone, were isolated from roots of Rollinia papilionella. The structure elucidation of rollinicin and isorollinicin was achieved through interpretation of the ¹H NMR, ¹³C NMR and high resolution mass spectra.     

Isolation and detailed 1H and 13C NMR structural assignment for three trachylobanes from Psiadia punctulata (Asteraceae) grown in Africa

The first isolation of a trachylobane from an African specimen of Psiadia punctulata (Asteraceae) is presented in this paper. A complete ¹H and ¹³C NMR spectral analysis of this compound and two other trachylobane diterpenes, previously isolated from the same plant, are also provided. The use of NMR techniques such as gCOSY, gHSQC, gHMBC and 2D-J-resolved, in combination with a software-assisted methodology, led to a complete and unequivocal assignment of ¹H and ¹³C signals. This was achieved together with the measurement of all homonuclear hydrogen coupling constants. The presented detail level of the assignment data has never been published before for trachylobanes. Furthermore, with all determined NMR experimental data from the spectra and to obtain a reliability assessment, signals were simulated in the FOMSC3 and NMR_MultSim software.     

1H, 13C and 199Hg NMR characteristics of new amine-mercuric chloride complexes

Reduction of some N-alkylimines has been achieved with NaBH₄ to give the corresponding secondary amines with high yields (85–95%). These amines were characterized on the bases of their ¹H and ¹³C NMR spectra. The reaction of these amines with mercuric chloride to afford the corresponding complexes was found to occur through a weak dative bond between the nitrogen lone pair of electrons and the mercury atom to form HgCl₂L₂ complexes. The ¹H, ¹³C and ¹⁹⁹Hg NMR chemical shifts have been obtained as well as ¹J(¹³CH) and ²J(¹³CH) coupling constants. Labelling with nitrogen-15 revealed that there is a weak coupling between the nitrogen and the ¹⁹⁹Hg.