A recent collection of Lepiota spiculata from the Dominican Republic is presented here. Macro- and micromorphological features of L. spiculata are described in detail, and its evolutionary (phylogenetic) position within Lepiota sect. Ovisporae, in the subincarnata/brunneoincarnata clade, is assessed on the basis of a combined nrLSU + nrITS + rpb2 + tef1 analysis. Additionally, high levels of deadly amatoxins were detected and quantified in L. spiculata for the first time by HPLC analysis; in particular, α-amanitin was found at concentrations up to approximately 4 mg/g dry weight, which render L. spiculata a potentially lethal mushroom, if ingested.
We present FQT4Web, a quantitative inspector-based methodology for Web site evaluation, with a hierarchical structure. A new approach, based on fuzzy operators, permits a sophisticated aggregation of measured atomic quality values, using linguistic criteria to express human experts' evaluations. A wide reference to standards and the limited number of subjective items increase the reliability of site analysis. This methodology has been fine-tuned for cultural sites; however, the assessment method is general-purpose. It is possible to obtain quality charts, which allow decision-makers to validate site quality on the basis of design goals.
Abstract 7-β-Thien-2-yl-acetamido-3-[(4-nitro-3-carboxyphenyl)thiomethyl]-3-cephem-4-carboxylic acid (CENTA) is a yellow chromogenic β-lactamases (BL) substrate. It hydrolyses readily in the presence of all BL and is therefore suitable for kinetic studies, the detection of BL enzymes in crude extracts and chromatographic fractions. CENTA is commercially available at a high price because of the cumbersome synthetic protocol, the only currently available for its preparation. Here we describe a new efficient and improved process for the preparation of CENTA. Starting from the easily available 7-aminocephalosporanic acid (7-ACA) through a three-step synthesis, CENTA was obtained with a 75% overall yield. The newly developed process proceeds through a pivotal intermediate in cephalosporin chemistry, which may be used as starting compound for the development of new cephalosporin derivatives.
The spring ascomycete Verpa bohemica − the “early morel” − has a long tradition of consumption in Emilia-Romagna (Northern Italy), where it is regularly collected, safely eaten and officially traded, as well as true morels (Morchella spp.). Unfortunately, V. bohemica is still listed among suspect or toxic mushrooms in most of North American and extra-European texts, despite the lack of analytical confirmation for the occurrence of toxins such as gyromitrin and coprine, which V. bohemica has been allegedly blamed for in the past, and in the absence of sound toxicological evidence as well. In fact, poisonings occasionally reported in the old literature after consumption of V. bohemica might have well been misunderstood with the so-called neurological syndrome associated with ingestion of Morchella spp. which has been formally described only in recent years. Mushroom collectors should therefore be reassured that V. bohemica and true morels share the very same edibility status. Riassunto L’ascomicete primaverile Verpa bohemica ha una lunga tradizione di utilizzo a scopo alimentare in Emilia-Romagna, dove viene regolarmente raccolto, consumato e commercializzato, alla stregua delle spugnole propriamente dette (Morchella spp.). Purtroppo V. bohemica continua ad essere elencata tra le specie sospette o tossiche nella maggior parte dei testi nordamericani ed extraeuropei, nonostante la mancanza di conferme analitiche della presunta presenza di tossine quali la giromitrina e la coprina per cui V. bohemica è stata accusata in passato, e anche in assenza di chiari indizi tossicologici. Infatti, i casi di intossicazione riportati in passato in letteratura a seguito del consumo di V. bohemica devono essere piuttosto ricondotti ad un’errata interpretazione della cosiddetta sindrome neurologica associata al consumo di funghi del genere Morchella che è stata correttamente caratterizzata solo in anni recenti. È pertanto necessario rassicurare i raccoglitori circa lo status di commestibilità di V. bohemica, che è da considerare assolutamente identico a quello delle vere spugnole. Figure 1. Verpa bohemica from Northern Upper Appennines (Farné near Lizzano in Belvedere (BO), Italy). Photo by Nicola Sitta. 4 FUNGI Volume 8:1 Spring 2015 Early Morels and Little Friars, or a Short Essay on the Edibility of Verpa bohemica Paolo Davoli a,* and Nicola Sitta b a via Pellegrini 2/18, 41058 Vignola (MO), Italy; e-mail: paolo-davoli@libero.it b Loc. Farné 32, 40042 Lizzano in Belvedere (BO), Italy; e-mail: nicolasitta@libero.it Mushrooms have featured an iconic role in Italian food tradition since time immemorial. There is plenty of historical evidence documenting the usage of mushrooms for food purposes by ancient Romans, who were particularly fond of boleti (Amanita caesarea) but did collect and also trade suilli, i.e. boletes (Boletus edulis and allied species) (Buller, 1914; Jaeger, 2011). Such a tradition of consumption has survived and further developed along the centuries in Italy, and the range of mushroom species that are used for food has meanwhile broadened. In fact, despite the fact that boletes (porcini in Italian) today represent the mushrooms par excellence in Italy and still account for most of the market share in mushroom trade (Sitta and Floriani, 2008), many edible fungal species other than porcini are widely collected and traded nationwide or on regional scale. Such is the case of true morels (Morchella spp.), which are most prized and actively sought after in the whole of Italy under the trivial name spugnole (= little sponges). Morel hunting and consumption in Italy does not reach the popularity as in the US or in France − Italian mushroom hunters and gourmands have a passion for porcini above all! Nonetheless it is tempting to speculate that the springtime appearance of potentially tasty food items such as morels, which could be used as accompaniments to otherwise plain cereal-based staple foods, must have represented a major drive for collection in ancient times. In this respect, however, it is not clear when consumption of morels first appeared in Italy. Some claimed that Pliny the Elder might have made an explicit reference to them in his Naturalis Historia (Maggiulli, 1977), but such a speculation is somewhat questionable in our opinion. On the contrary, it is most likely that the first ever documentary evidence clearly describing the usage of morels for food purposes in Italy can be traced back to the Late Middle Ages. In addition to true morels, in EmiliaRomagna (Northern Italy) also Verpa bohemica (Krombh.) J. Schröt. (Figs. 1−3) has a long tradition of consumption and it is even traded officially on a local scale (Figs. 4−5). In the province of Modena V. bohemica fruits from March to early May, sometimes abundantly, whereas true morels appear two or three weeks later, under conditions of same elevation and slope orientation; V. bohemica grows under several species of broadleaved trees, in particular elms (Ulmus spp.), poplars (Populus spp.) and willows (Salix spp.), often along rivers and streams, and often hidden in dense thickets of bramble and wild roses (Rubus spp. and Rosa spp., respectively) in the understory. In moisture-rich locations it can also grow abundantly in degraded chestnut or beech woods, especially at the edge, or close to ruins of buildings and stone walls. Its distribution range spans from the foothills of Lower Appennines (and adjacent areas bordering the river Po plain) to the Upper Appennines, up to elevations of ca. 1500 m above sea level. Known as the “early morel” in EnglishFigure 2. Verpa bohemica from Northern Lower Appennines (Vignola (MO), Italy). Photo by Paolo Davoli. 5 FUNGI Volume 8:1 Spring 2015 Figure 3. Verpa bohemica from Northern Lower Appennines (Vignola (MO), Italy). Photo by Paolo Davoli. speaking countries, in the province of Modena V. bohemica is usually referred to as fratèin in the local dialect (in Italian it translates as fratino, i.e. little friar), whilst true morels are collectively called sfuracèli instead (Bellei, 1999); sometimes the name frê (in Italian frate = friar) is also used for V. bohemica. By close analogy, the trivial names fratèin/frê are often applied locally also to Mitrophora semilibera (DC.) Lév. (syn. Morchella semilibera DC.). (Bellei and Benatti Spennato, 1994). It is worthy to note − at least from an ethnomycological viewpoint − that Helvella crispa (Scop.) Fr. is called in the local dialect surèina and pritèin (corresponding to Italian suorina and pretino) (San Donnini, 1899), i.e. little nun and little priest, respectively. In the US Verpa bohemica is usually regarded as suspect or toxic by many field guides; even when it is reported as edible, it is generally not recommended for eating and caution is always given that it may cause gastrointestinal discomfort in some people. According to Beug et al. (2014), V. bohemica is “edible for some but poisonous to many others, causing variable reactions, including severe gastrointestinal upset and temporary loss of coordination.” Similar information about the toxicity of early morels can be found on mushroom books aimed at a worldwide audience (e.g. Hall et al., 2003; Roberts and Evans, 2011) and also in some (albeit few!) Italian and European field guides, even though most of them always list V. bohemica as edible, and rightly so. In the FAO’s compendium of wild edible mushrooms, V. bohemica is included in the global list of wild fungi used as food, and it is also listed between the “economically important wild fungi” (Boa, 2004). Also to the best of our knowledge V. bohemica can be safely eaten and it should therefore be included among edible fungal species. Accordingly, in Emilia-Romagna it is officially included at a regional level in the positive list of edible mushrooms allowed for trade (Italy, 1995; Emilia-Romagna, 1997). Clearly, it is one of those cases of contrasting evaluation of edibility that are often found in the (ethno)mycological literature (see Sitta and Davoli, 2012). At least as far as the North American mycological literature is concerned, we believe that such a confusion about the edibility of V. bohemica stems from Lincoff and Mitchel’s Toxic and Hallucinogenic Mushroom Poisoning (1977), an authoritative source of mycotoxicological information that still represents a leading reference in the field and which has been frequently quoted by mycologists in subsequent decades. In fact, Lincoff and Mitchel, quoting earlier and scattered cases of poisonings caused by ingestion of early morels, wrote: “...it is possible that Verpa bohemica, or certain strains or fruiting of it, contain or can synthesize low levels of gyromitrin.” (Lincoff and Mitchel, 1977). To the best of our knowledge, however, the presence of gyromitrin in V. bohemica has never been demonstrated experimentally. Despite thorough bibliographical searches, we could not find a single reference that confirms unambiguously the detection of gyromitrin and analogues thereof in V. bohemica, neither before nor after the publication of Lincoff and Mitchel’s book. Nonetheless their view has certainly consolidated over the years and must have remained widely accepted in the US and elsewhere. We wonder about the official status of V. bohemica in the US. For instance, is it allowed for 6 FUNGI Volume 8:1 Spring 2015 Figure 5. Close-up of a basketful of Verpa bohemica ready to be offered for sale. Photo by Paolo Davoli. trade? As far as we know, according to the FDA, V. bohemica is lumped with Gyromitra spp. and Helvella spp., and all of them are considered toxic (FDA, 1984; Gecan and Cichowicz, 1993). We have found official reports from the FDA whereby detection of V. bohemica in consignments of dried and canned morels for US import resulted in noncompliance of the shipment and failure to obtain custom clearance (see for example FDA Import Alert 25-02, 2011). Caution is certainly required when dealing with Gyromitra, but o
Cupreoboletus is erected as a new monospecific genus of Boletaceae to accommodate the thermophilic southern European species Boletus poikilochromus, characterized by discoloration toward copper-red tints overall, hymenophore forming tiny crystals on drying, a pervasive and long lasting sweet odor and presence of pseudocystidia. Macro- and microscopic descriptions of the species based on re-examination of the type material and recent Italian collections including additional topotypical samples are provided and accompanied by photos and line drawings of the main anatomical structures. In addition, an epitype specimen is selected. Phylogenetic relationships were inferred from multigene molecular analysis based on partial sequences of the nuc rDNA 28S D1/D2 (28S) and internal transcribed spacer (ITS) regions and genes for ribosomal RNA polymerase II subunits 1 (rpb1) and 2 (rpb2) and translation-elongation factor 1-α (tef1α). Ecological context, geographical range and delimitation from closely allied taxa also were elucidated. B. martaluciae is treated as a synonym of C. poikilochromus according to the morphological and molecular comparative study.
Diversely functionalized imidazole-4-carboxylates were synthesized by microwave-assisted 1,5-eletrocyclization of 1,2-diaza-1,3-diene-derived azavinyl azomethine ylides 1,2-Diaza-1,3-dienes were treated with primary aliphatic or aromatic amines and subjected to microwave irradiation in the presence of aldehydes 3-Alkyl- and 3-arylimidazole-4-carboxylates were prepared in good yields through a one-pot multicomponent procedure. Modulation of the substituents at C-2, N-3, and C-5 was possible, and 2-unsubstituted Imidazoles were obtained when paraformaldehyde was used
Substituted beta-phenylethylamides undergo smooth intramolecular cyclization to 3,4-dihydroisoquinolines in good to excellent yields when treated with bromotriphenoxyphosphonium bromide at -60 degrees C in dichloromethane in the presence of triethylamine. The reaction proceeds under the mildest conditions ever reported for Bischler-Napieralski-type cyclizations. When chlorotriphenoxyphosphonium choride is used, low yields are obtained instead.
The importance of groupware tools in e-learning practice is increasing, because of their educational relevance and of the importance of group abilities in today's job activities. The paper addresses some critical issues of asynchronous collaborative tools hosted in Web-learning platforms. A model to capture user quality perceptions for these tools is presented, and an investigation conducted in three case studies where e-learning platforms were used to share and comment on written works is reported in detail. Quantitative and qualitative data are used in a complementary way to capture the complexity of educational collaborative activities. The impact of technologies on work organization, writing and peer-feedback activities is discussed. Users dedicated more time to feedback activities than they would have in real-life contexts, and paid more attention to the style and content of their writing. Communication was more focused and honest than in real life (even though more distant and at the risk of misunderstanding), and its indirectness encouraged shy and impaired people. Usability problems emerged from platform design, educators' choices and server-side settings; Web-based systems seem to pose specific usability issues when users are required a strong active role; compatibility issues highlight the need for a closer Web standard compliance.
An efficient and practical method for the preparation of alpha-imidazol-1-yl esters from 1,2-diaza-1,3-dienes (DDs), alpha-amino esters, and aldehydes is described. The overall sequence features a Michael-type conjugate addition between the alpha-amino ester and the DD, followed by iminium ion formation via condensation with the aldehyde and 1,5-electrocyclization of the resulting thermally generated azavinyl azomethine ylide to afford eventually alpha-imidazol-1-yl esters. Such a protocol allows access to enantiomerically pure imidazoles from optically pure alpha-amino esters.
Atom transfer radical cyclization (ATRC) of N-alkyl N-allyl dichloroamides to gamma-lactams, catalyzed by `naked' CuCl, worked efficiently in DMF, whereas, when the same dichloroamides were N-sulfonylated, DMF needed to be replaced by acetonitrile. The outcome of the cycloisomerization with N-substituted N-allyl trichloroacetamides was less affected by solvent choice, although for an effective reaction to occur, the solvent had to dissolve the cuprous salt. Catalyst loading ranged between 5 and 20 mol%.
A mild procedure for the synthesis of aromatic and aliphatic nitriles is disclosed. In the presence of bromotriphenoxy-phosphonium bromide (TPPBr(2)), N-alkyl and N,N-dialkyl amides undergo von Braun degradation to nitriles in good to excellent yields under the mildest conditions ever reported. The reaction proceeds via formation of an iminoyl bromide intermediate at -60 degrees C, which subsequently dealkylate upon refluxing in chloroform or even at room temperature. In the case of N-tert-butyl, N-alpha-phenylethyl and N-benzhydryl amides, chlorotriphenoxyphosphonium chloride (TPPCl(2)) generated at -30 degrees C was also effective.
A simple method for the extraction of carotenoid pigments from frozen wet cells of red yeasts (Basidiomycota) and their analysis by reversed-phase HPLC using a C18 column and a water/acetone solvent system is described. Typical red yeast carotenoids belonging to an oxidative series from the monocyclic γ-carotene to 2-hydroxytorularhodin and from the bicyclic β-carotene to astaxanthin were separated. Pigment identity was confirmed by LC–atmospheric pressure chemical ionisation (APCI) mass spectrometry using similar chromatographic conditions.
Two red Cystofilobasidium spp. isolated from spring sap-flows of Betula pendula were analysed for their carotenoid content. In Cystofilobasidium infirmominiatum, three unusual pigments were detected and identified by structure elucidation as oxidised torulene derivatives. These included 16'-hydroxytorulene and torularhodinaldehyde, two carotenoids known so far only from chemical synthesis or as postulated biosynthetic intermediates en route to torularhodin. Unprecedented formation of beta-apo-2'-carotenal was also observed. The production of these pigments in pure culture was dependent on enhanced oxidative stress caused by cultivation in well-aerated (indented) flasks with or without 2% ethanol (16'-hydroxytorulene), or with 100 microM duroquinone (torularhodinaldehyde and beta-apo-2'-carotenal). Among these three pigments, only 16'-hydroxytorulene was detected in C. capitatum. Torularhodin, a common end product of carotenoid oxidation in red yeasts, was not produced by either species under any incubation conditions. Biosynthetic aspects of incomplete oxidation of torulene by these Cystofilobasidium spp. are discussed.
An expeditious route to nitriles via dehydration of primary amides using halotriphenoxy phosphonium halides (TPPX2, X = Cl or Br) is described. The reaction proceeds under very mild conditions and allows the preparation of aromatic and aliphatic nitriles in good to excellent yields.
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.
A new application of (PhO)3P-halogen-based reagents to the synthesis of vinyl halides and gem-dihalides is described. Vinyl halides were prepared in good to excellent yields from enolizable ketones, whereas aldehydes afforded the corresponding gem-dihalides. The halogenation proceeded smoothly under mild conditions.
Xanthophyllomyces sp. was isolated as an epiphytic red yeast from leaves of Eucalyptus glo-bulus in Concepción, Chile. Sexual reproduction was by basidiospores produced from one or rarely two metabasidia arising from a yeast cell without preceding paedogamy. The main carotenoid pigment was astaxanthin. This isolate did not cluster with the X. dendrorhous complex (including Phaffia rhodozyma) in ITS and 26S rDNA-based phylogenetic analyses. The phylloplane may be a further habitat for Xanthophyllomyces, in addition to the well-known spring sap-flows of deciduous trees and the recently-characterised ascostromata of Cyttaria hariotii.
Michael-type addition of aziridinecarboxylates to 1,2-diaza-1,3-butadienes under solvent-free conditions (SFC) resulted in the formation of alpha-aziridinohydrazone adducts. In toluene under reflux, alpha-aziridinohydrazones gave imidazoles in moderate to good yields. Such a reactivity pattern is explained by 1,5-electrocyclization of azavinyl azomethine ylide generated through thermal ring opening of alpha-aziridinohydrazones.