Past climate cooling promoted global dispersal of amphipods from Tian Shan montane lakes to circumboreal lakes.

Climate changes have substantial impacts on the geographic distribution of montane lakes and evolutionary dynamics of cold-adapted species. Past climate cooling is hypothesized to have promoted the dispersal of cold-adapted species via montane lakes, while future climate warming is thought to constrain their distributions. We test this hypothesis by using phylogeographic analysis and niche modeling of the Holarctic crustacean Gammarus lacustris with global sampling comprised of 567 sequenced individuals and 3180 occurrence records. We found that the species arose in Tian Shan in Central Asia and dispersed into montane lakes along the Alps, Himalayas, Tibet, East Asia, and the North American Rocky Mountain ranges, with accelerated diversification rates outside Tian Shan. Climatically suitable regions for geographic lineages of G. lacustris were larger during cooling periods (LGM), but smaller during warming periods (Mid-Holocene). In the future (2070) scenario, potential distributions in the Himalayas, North Tibet, South Tibet and North America are predicted to expand, whereas ranges in East Asia, Europe and Tian Shan will decline. Our results suggest that Mid-Miocene-to-Pleistocene continuous cooling promoted multiple independent dispersal events out of Tian Shan due to increased availability of montane lakes via "budding" of lineages. Montane lakes are conduits through which cold-adapted amphipods globally dispersed, dominating circumboreal lakes. However, future climate warming is likely to force organisms to shift upward in altitude and northward in latitude, leading to a future change in local populations. These findings highlight the importance of conservation of montane lakes, especially in the context of climate change.

Photodegradation of methoxy substituted curcuminoids.

Photodegradation of dimethoxy curcuminoids in acetonitrile solution was found to depend on the position of the methoxy group bonded to the phenyl ring. The rate of decomposition was expressed as the lifetime of the decomposing substrate, being the shortest in the case of the 3,5-dimethoxy and the longest for the 2,5-dimethoxy derivative. For the 3,5-dimethoxy curcuminoid, the major degradation products were 3,5-dimethoxy benzaldehyde, 3,5-dimethoxybenzoic acid and the Z and E isomers of dimethoxy cinnamic acid, together forming about 90% of the reaction mixture. Minor products found were 4,5-bis(3,5-dimethoxyphenyl)hex-2-endionic acid, and products with the molecular formula C23H24O6 and C23H22O6 attributed to the reaction of intramolecular [2+2] cycloaddition of the dimethoxy curcuminoid and the dioxygenated bicyclopentadione derivative (C23H24O8) derived from autoxidative transformation of the dimethoxy curcuminoid.

Crystal structures and emission properties of the BF2 complex 1-phenyl-3-(3,5-dimethoxyphenyl)-propane-1,3-dione: multiple chromisms, aggregation- or crystallization-induced emission, and the self-assembly effect.

It is known that electron donating groups have quite a different effect on the π-delocalization of a conjugate system when bonded at ortho and para as compared to meta positions in the phenyl ring. In the present work, the BF2 complex of 1-phenyl-3-(3,5-dimethoxyphenyl)-propane-1,3-dione (1), a molecule with two methoxy groups in one of the phenyl rings at meta positions, was prepared. Compound 1 exists as two polymorphs having different mutual orientations of the two methoxy groups: in polymorph A away from each other (termed anti), while in polymorph B one methoxy group is oriented toward the other (syn-anti). In both crystals, the molecules which are antiparallel (the subPh rings as well as dioxaborine are on opposite sides) form stacks through face-to-face π-π interactions, while in polymorph A the crystal packing is further stabilized by intermolecular C(phenyl)-H···F and C(methoxy)-H···F hydrogen bonds. Solid A possesses numerous chromic effects, including mechano-, thermo-, and chronochromism, though the latter to a lesser extent, as well as the effect of rearrangement of the amorphous phase into a more stable crystalline phase A, associated with crystallization-induced emission enhancement (CIEE). The solid-state emission can be repeatedly switched regarding its color and efficiency with excellent reversibility by external stimuli. On the other hand, crystalline solid B undergoes thermal interconversion of syn-anti to the anti conformer. Compound 1 shows a solvatochromic effect (SE), is aggregation-induced emission (AIE) active, and through the sublimation process displays self-assembling crystalline platelike microstructures or microfibers that reveal an obvious optical waveguide effect.

Phylogenetic analyses of Gammaridae crustacean reveal different diversification patterns among sister lineages in the Tethyan region.

The Gammaridae shows the greatest disparity in species diversity and distribution pattern in the Amphipoda, with some genera ranging from the Palearctic to Nearctic, while others are limited to the Mediterranean region or ancient Tethyan margins. Here we present the first molecular phylogenetic analysis of the Gammaridae to investigate its evolutionary history using four genetic markers and a comprehensive set of taxa representing 198 species. The phylogenetic results revealed that the Gammaridae originated from the Tethyan region in the Cretaceous, and split into three morphologically and geographically distinct lineages by the end of the Paleocene. Diversification analysis combined with paleogeological evidence suggested that the Tethyan changes induced by sea-level fluctuation and tectonic uplift triggered different diversification modes and range expansions for the three lineages. The Gammarus lineage underwent an early rapid radiation across Eurasia and North America, then declined towards modern species. Pontogammarids maintained stable diversification with restricted distributions around the Tethyan basin, whereas sarothrogammarids experienced evolutionary stasis by stranding on the ancient Tethyan margins. Our findings suggest that environmental changes have played an important role in the diversification of Gammaridae lineages, which could be an opportunity to promote adaptive radiations in new habitats, or constraints resulting in evolutionary relicts.

Eocene habitat shift from saline to freshwater promoted Tethyan amphipod diversification.

Current theory predicts that a shift to a new habitat would increase the rate of diversification, while as lineages evolve into multiple species, intensified competition would decrease the rate of diversification. We used Holarctic amphipods of the genus Gammarus to test this hypothesis. We sequenced four genes (5,088 bp) for 289 samples representing 115 Gammarus species. A phylogenetic analysis showed that Gammarus originated from the Tethyan region with a saline ancestry in the Paleocene, and later colonized the freshwater habitat in the Middle Eocene. Ancestral range reconstruction and diversification mode analysis combined with paleogeological and paleoclimatic evidence suggested that the habitat shift from saline to freshwater led to an increased diversification rate. The saline lineage of Gammarus dispersed to both sides of the Atlantic at 55 million years ago (Ma), because of the few barriers between the Tethys and the Atlantic, and diversified throughout its evolutionary history with a constant diversification rate [0.04 species per million years (sp/My)]. The freshwater Gammarus, however, underwent a rapid diversification phase (0.11 sp/My) until the Middle Miocene, and lineages successively diversified across Eurasia via vicariance process likely driven by changes of the Tethys and landmass. In particular, the freshwater Gammarus lacustris and Gammarus balcanicus lineages had a relatively high diversification shift, corresponding to the regression of the Paratethys Sea and the continentalization of Eurasian lands during the Miocene period. Subsequently (14 Ma), the diversification rate of the freshwater Gammarus decreased to 0.05 and again to 0.01 sp/My. The genus Gammarus provides an excellent aquatic case supporting the hypothesis that ecological opportunities promote diversification.

A collaborative backbone resource for comparative studies of subterranean evolution: The World Asellidae database.

Transition to novel environments, such as groundwater colonization by surface organisms, provides an excellent research ground to study phenotypic evolution. However, interspecific comparative studies on evolution to groundwater life are few because of the challenge in assembling large ecological and molecular resources for species-rich taxa comprised of surface and subterranean species. Here, we make available to the scientific community an operational set of working tools and resources for the Asellidae, a family of freshwater isopods containing hundreds of surface and subterranean species. First, we release the World Asellidae database (WAD) and its web application, a sustainable and FAIR solution to producing and sharing data and biological material. WAD provides access to thousands of species occurrences, specimens, DNA extracts and DNA sequences with rich metadata ensuring full scientific traceability. Second, we perform a large-scale dated phylogenetic reconstruction of Asellidae to support phylogenetic comparative analyses. Of 424 terminal branches, we identify 34 pairs of surface and subterranean species representing independent replicates of the transition from surface water to groundwater. Third, we exemplify the usefulness of WAD for documenting phenotypic shifts associated with colonization of subterranean habitats. We provide the first phylogenetically controlled evidence that body size of males decreases relative to that of females upon groundwater colonization, suggesting competition for rare receptive females selects for smaller, more agile males in groundwater. By making these tools and resources widely accessible, we open up new opportunities for exploring how phenotypic traits evolve in response to changes in selective pressures and trade-offs during groundwater colonization.

Structure and community composition of sprout-like bacterial aggregates in a Dinaric Karst subterranean stream.

The Vjetrenica cave in the Dinaric Karst hosts a worldwide extraordinarily high cave biodiversity. Beside a diverse and specialized cave fauna, sprout-like formations attached to the bed of the cave stream were observed and described, but not further characterized, almost a century ago. Here we investigated these sprout-like microbial aggregates by the rRNA approach and detailed microscopy. Based on fluorescence in situ hybridization and ultrastructural analysis, the sprout-like formations are morphologically highly organized, and their core consists of a member of a novel deep-branching lineage in the bacterial phylum Nitrospirae. This organism displays an interesting cellular ultrastructure with different kinds of cytoplasmic inclusions and is embedded in a thick extracellular matrix, which contributes to the stability and shape of the aggregates. This novel bacterium has been provisionally classified as "Candidatus Troglogloea absoloni." The surface of the sprout-like aggregates is more diverse than the core. It is colonized by a bacterial biofilm consisting primarily of filamentous Betaproteobacteria, whereas other microbial populations present in the crust include members of the Bacteriodetes, Gammaproteobacteria, Actinombacteria, Alphaproteobacteria, and Planctomycetes, which are intermingled with mineral inclusions. This study represents the first thorough molecular and ultrastructural characterization of the elusive sprout-like bacterial aggregates, which are also found in other cave systems of the Dinaric Karst. The discovery of Ca. Troglogloea absoloni contributes to the known biodiversity of subterranean ecosystems and especially of macroscopic structures formed in caves by microorganisms, whose composition and ecological function often remain enigmatic.

A corrigendum to the phylogeny of the family Gammaridae (Crustacea: Amphipoda).

We stated an error in our previous DNA analysis of Gammaridae. The right position of Zenkevitchia in the phylogenetic tree is close to marine and American Gammarus spp., far from the Dinaric troglobiotic Typhlogammarus group of genera. The morphologically diverse Zenkevitchia group supports the necessity of some paraphyly in systematics.

The limits of cryptic diversity in groundwater: phylogeography of the cave shrimp Troglocaris anophthalmus (Crustacea: Decapoda: Atyidae).

Recent studies have revealed high local diversity and endemism in groundwaters, and showed that species with large ranges are extremely rare. One of such species is the cave shrimp Troglocaris anophthalmus from the Dinaric Karst on the western Balkan Peninsula, apparently uniform across a range of more than 500 kilometers. As such it contradicts the paradigm that subterranean organisms form localized, long-term stable populations that cannot disperse over long distances. We tested it for possible cryptic diversity and/or unexpected evolutionary processes, analysing mitochondrial (COI, 16S rRNA) and nuclear (ITS2) genes of 232 specimens from the entire range. The results of an array of phylogeographical procedures congruently suggested that the picture of a widespread, continuously distributed and homogenous T. anophthalmus was wrong. The taxon is composed of four or possibly five monophyletic, geographically defined phylogroups that meet several species delimitation criteria, two of them showing evidence of biological reproductive isolation in sympatry. COI genetic distances between phylogroups turned out to be a poor predictor, as they were much lower than the sometimes suggested crustacean threshold value of 0.16 substitutions per site. Most results confirmed the nondispersal hypothesis of subterranean fauna, but the southern Adriatic phylogroup displayed a paradoxical pattern of recent dispersal across 300 kilometers of hydrographically fragmented karst terrain. We suggest a model of migration under extreme water-level conditions, when flooded poljes could act as stepping-stones. In the north of the range (Slovenia), the results confirmed the existence of a zone of unique biogeographical conflict, where surface fauna is concordant with the current watershed, and subterranean fauna is not.

New genus and species of the family Niphargidae (Crustacea: Amphipoda: Senticaudata), Chaetoniphargus lubuskensis gen. nov., sp. nov. from Croatia.

New genus and species of the family Niphargidae (Crustacea: Amphipoda: Senticaudata), Chaetoniphargus lubuskensis gen. nov., sp. nov. from the subterranean waters of cave Lubuska jama near Hajducki Kukovi in the western part of Velebit Mt. in Croatia, is described and figured, and its relations to other genera and species of the family Niphargidae is discussed. The new taxon is a small niphargid, similar to Niphargobates. The list of all known genera of family Niphargidae is given and key to the genera of this family is presented.

Three new remarkable amphipod species (Crustacea: Gammaridae) from springs and subterranean waters of Central Asia.

Three new species of the family Gammaridae-Gammarus troglomorphus, sp. n., G. parvioculatus, sp. n. from Lebap Province of Turkmenistan and Tadzocrangonyx alaicus, sp. n. from Batken Region of Kyrgyzstan are described and illustrated. Morphological studies of a closely related Turkmenistan population of G. cf. subaequalis-Garlyk, probably conspecific with Gammarus subaequalis Martynov, 1935 was provided. The affinity of new species to concerned taxa is discussed. To define phylogenetic position of mentioned species DNA barcode data are obtained. Gammarus troglomorphus and G. parvioculatus are close neighbors but exceedingly different morphologically. Gammarus troglomorphus is a troglobiont; G. parvioculatus is an eutroglophile, but with exception of slightly smaller eyes, not troglomorph. Both found only within small areas in the extreme East of Turkmenistan. Gammarus cf. subaequalis-Garlyk seems to extend from the same region far into the eastern Kyrgyzstan.

Phylogenetic relationships of the Balkan Moitessieriidae (Caenogastropoda: Truncatelloidea).

The family Moitessieriidae includes minute dioecious gastropods exclusively inhabiting subterranean waters, including thermal ones. Only empty shells were collected in most species, the vast majority of them are described from their gross shell morphology alone. Several visits to a site are usually required to obtain at least some living individuals. High variability in shell morphology and the lack of diagnostic features, coupled with anticipated high levels of endemism, has resulted in a long list of nominal moitessierid species. Type specimens stored as empty shells omit unambiguous identification and delimitation of species boundaries. Due to inaccessibility of cave animals and consequent lack of material suitable for molecular analysis, the phylogenetic relationships, as well as the taxonomy of the family at genus/species level, are far from being understood. The anatomy of the family is also poorly known and provided only for a few taxa. The distinctness of the Moitessieriidae has sometimes been questioned, and their monophyly not proved. Twelve species of the Balkan Moitessieriidae are considered: two species of Paladilhiopsis, two species of Bythiospeum, six species of Iglica, Costellina turrita and Lanzaia bosnica. The shell morphology of each species, as well as the reproductive system of Paladilhiopsis and Iglica, were analysed. DNA sequences of nuclear histone H3, ribosomal 18S, ribosomal 28S and mitochondrial cytochrome oxidase subunit I (COI) were applied to infer phylogenetic relationships among the taxa. The sequences of Bythiospeum from GenBank have been used to infer relationships between Bythiospeum and Paladilhiopsis that were recently synonymized. Paladilhiopsis and Iglica are distinct, but closely related genera, as is the genus Bythiospeum, which does not occur in the Balkans. Its relationships with both former taxa remain unresolved. The Moitessieriidae are clearly distinct from all other families of the Truncatelloidea, however, their monophyly remains doubtful.

Photocyclization of 2-chloro-substituted 1,3-diarylpropan-1,3-diones to flavones.

The photochemical behavior of 2-halo-substituted 1,3-diarylpropan-1,3-dione strongly depends on the nature of the halogen atom bonded and the presence of electron-donor groups on the phenyl ring. In the case of 2-chloro-1,3-diphenylpropan-1,3-dione and 1-(3,5-dimethoxyphenyl)-3-phenylpropan-1,3-dione, cyclization to flavones was the sole reaction pathway, whereas in the case of 2-chloro-1,3-di(4-methoxyphenyl)propan-1,3-dione, only products derived from alpha-cleavage were observed. 2-Fluoro derivatives of 1,3-diarylpropan-1,3-diones were photostable; on the other hand, 2-chloro-2-fluoro derivates resulted in 3-fluoroflavones.

The first Turcolana Argano & Pesce, 1980 (Isopoda: Cirolanidae) from the Greek mainland.

Turcolana Argano & Pesce, 1980 is the isopod genus occurring in freshwater and brackish groundwater environments around the eastern Mediterranean. In this study, a revised diagnosis of the genus, an updated map of species distribution and a key to species are presented. The first cave dwelling species is described from the Melissotrypa Cave in central Greece, a highly troglomorphic Turcolana lepturoides sp. nov. Its principal distinguishing characters are elongated appendages: styliform uropods (twice as long as pleotelson), antennae (half as long as body) and pereopods (e.g. pereopod 7 45% as long as body). Mitochondrial DNA sequences (16S rRNA, 12S rRNA) of the new species are provided.

Melita mirzajanii n. sp. (Crustacea: Amphipoda: Melitidae), a puzzling new member of the Caspian fauna.

Described is Melita mirzajanii n. sp. (Melitidae) from the southwestern corner of the Caspian Sea. It shows no particular similarity to any species known from the Mediterranean Sea. It inhabits, as the only amphipod species, dense growths of Amphibalanus cf. improvisus (Darwin 1854) in a port, at low and highly fluctuating salinities. Its most striking characters are: absence of any pleonal or urosomal dorsal teeth (projections), elongated distal article of the mandibular palp, hind margin of last pereopod bases strongly narrowed distad, and epimera posterodistally rectangular. An identification key for the species group of Melita without dorsal teeth and without article 2 on the exopodite of the third uropod is provided.

Fauna Europaea: Annelida - Hirudinea, incl. Acanthobdellea and Branchiobdellea.

Fauna Europaea provides a public web-service with an index of scientific names (including important synonyms) of all living European land and freshwater animals, their geographical distribution at country level (up to the Urals, excluding the Caucasus region), and some additional information. The Fauna Europaea project covers about 230,000 taxonomic names, including 130,000 accepted species and 14,000 accepted subspecies, which is much more than the originally projected number of 100,000 species. This represents a huge effort by more than 400 contributing specialists throughout Europe and is a unique (standard) reference suitable for many users in science, government, industry, nature conservation and education. Hirudinea is a fairly small group of Annelida, with about 680 described species, most of which live in freshwater habitats, but several species are (sub)terrestrial or marine. In the Fauna Europaea database the taxon is represented by 87 species in 6 families. Two closely related groups, currently treated as distinct lineages within the Annelida, are the Acanthobdellea (2 species worldwide, of which 1 in Europe) and the Branchiobdellea (about 140 species worldwide, of which 10 in Europe). This paper includes a complete list of European taxa belonging to the Hirudinea, Acanthobdellea and Branchiobdellea. Recent research on a limited number of taxa suggests that our current appreciation of species diversity of Hirudinea in Europe is still provisional: on the one hand, cryptic, unrecognised taxa are expected to emerge; on the other, the status of some taxa currently treated as distinct species deserves revisiting.

Structures in solid state and solution of dimethoxy curcuminoids: regioselective bromination and chlorination.

BACKGROUND: Several papers described the structure of curcumin and some other derivatives in solid and in solution. In the crystal structure of curcumin, the enol H atom is located symmetrically between both oxygen atoms of the enolone fragment with an O···O distance of 2.455 Å, which is characteristic for symmetrical H-bonds. In the solution, the geometry of the enolone fragment is attributed to the inherent disorder of the local environment, which solvates one of the basic sites better than the other, stabilizing one tautomer over the other. In this paper, how the position of methoxy groups in dimethoxy curcuminoids influence the conformation of molecules and how the halogen atoms change it when they are bonded at α-position in keto-enol part of molecules is described. RESULTS: Six isomers of dimethoxy curcuminoids were prepared. Conformations in solid state, which were determined by X-ray single crystallography and 1H MAS and 13C CPMAS NMR measurements, depend on the position of methoxy groups in curcuminoid molecules. In solution, a fast equilibrium between both keto-enol forms exists. A theoretical calculation finding shows that the position of methoxy groups changes the energy of HOMO and LUMO. An efficient protocol for the highly regioselective bromination and chlorination leading to α-halogenated product has been developed. All α-halogenated compounds are present mainly in cis keto-enol form. CONCLUSIONS: The structures in solid state of dimethoxy curcuminoids depend on the position of methoxy groups. The NMR data of crystalline solid samples of 3,4-diOCH3 derivative, XRD measurements and X-ray structures lead us to the conclusion that polymorphism exists in solids. The same conclusion can be done for 3,5-diOCH3 derivative. In solution, dimethoxy curcuminoids are present in the forms that can be described as the coexistence of two equivalent tautomers being in fast equilibrium. The position of methoxy groups has a small influence on the enolic hydrogen bond. Theoretical calculations show that the energy gap between HOMO and LUMO depend on the position of methoxy groups and are lower in solution. Chlorination and bromination on α-position of 1,3-diketone moiety do not change the preferential form being cis keto-enol as in parent compounds.

Diversity of microbial communities colonizing the walls of a Karstic cave in Slovenia.

Karstic cave systems in Slovenia receive substantial amounts of organic input from adjacent forest and freshwater systems. These caves host microbial communities that consist of distinct small colonies differing in colour and shape. Visible to the naked eye, the colonies cover cave walls and are strewn with light-reflecting water droplets. In this study, the diversity of prokaryotes constituting these unusual microbial communities in Pajsarjeva jama cave was examined. A molecular survey based on small subunit rRNA diversity showed a high diversity within the Bacteria, while members of Archaea were not recovered. A total of eight bacterial phyla were detected. The application of various species richness estimators confirmed the diverse nature of the microbial community sample. Members of Gammaproteobacteria were most abundant in the clone libraries constructed and were followed in abundance by members of Actinobacteria and Nitrospira. In addition, members of Alphaproteobacteria, Betaproteobacteria and Deltaproteobacteria as well as Acidobacteria, Verrucomicrobia, Planctomycetes, Chloroflexi and Gemmatimonadetes were identified in clone libraries. The high number of clones most closely related to environmental 16S rRNA gene clones showed the broad spectrum of unknown and yet to be cultivated microorganisms inhabiting these cave systems.

Phylogeny of the cave shrimp Troglocaris: Evidence of a young connection between Balkans and Caucasus.

The remarkably discontinuous distribution of the cave shrimp genus Troglocaris in South France, West Balkans, and West Caucasus has long been considered a biogeographic enigma. To solve it, its phylogeny was reconstructed by analyzing sequences from two mitochondrial (cytochrome oxidase I and 16S rRNA) and one nuclear gene (28S rRNA) using maximum likelihood, parsimony and Bayesian inference. The genus was found to be polyphyletic because the French taxon T. inermis had no direct common ancestry with other Troglocaris taxa but was sister to the epigean freshwater atyid Dugastella valentina. All other Troglocaris species constituted a well-supported monophylum, the second cave shrimp genus Spelaeocaris nested within. The monophylum had a well-defined structure: (1) a clade restricted to the Dinaric area of the Western Balkans containing the type species T. anophthalmus along with some unnamed species, and (2) a geographically mixed clade split between the Caucasian T. kutaissiana species complex on one, and T. hercegovinensis, S. pretneri, plus an unnamed taxon on the other side. It was surprising to find the dichotomy between the Caucasian and one of the West-Balkan lineages so low in the phylogenetic hierarchy of the genus. Taking into account molecular rates of other decapods, we tentatively dated this split at 6-11 Myr. This time is in agreement with the brackish and freshwater phase of the Paratethys thus allowing for a freshwater common ancestor of Caucasian and Dinaric cave shrimps. This would weaken the marine relicts hypothesis that has often been invoked to explain the distribution of freshwater cave species with close marine relatives.

Primary photoreactions of the 3',5'-dimethoxybenzoin cage and determination of the release rate in polar media.

3',5'-dimethoxybenzoin (DMB) is an important photoremovable protecting group. The primary photoreactions of DMB acetate and fluoride following photoexcitation by a subpicosecond laser flash were investigated by pump-probe spectroscopy. The primary photoproduct is identified as a preoxetane biradical intermediate that decays by different pathways depending on solvent polarity. In polar solvents (acetonitrile, water), the biradical decays by releasing acetate or fluoride with a lifetime of about 2 ns. Thus, DMB is an excellent protecting group for the investigation of fast processes such as protein folding.