Ab initio and density functional theory calculations at the B3-MP2 and CCSD(T)/6-311 ϩ G(3df,2p) levels of theory are reported that address the protonation of adenine in the gas phase, water clusters, and bulk aqueous solution. The calculations point to N-1-protonated adenine (1 ؉ ) as the thermodynamically most stable cationic tautomer in the gas phase, water clusters, and bulk solution. This strongly indicates that electrospray ionization of adenine solutions produces tautomer 1 ؉ with a specificity calculated as 97-90% in the 298 -473 K temperature range. The mechanisms for elimination of hydrogen atoms and ammonia from 1 ؉ have also been studied computationally. Ion 1 ؉ is calculated to undergo fast migrations of protons among positions N-1, C-2, N-3, N-10, N-7, and C-8 that result in an exchange of five hydrogens before loss of a hydrogen atom forming adenine cation radical at 415 kJ mol Ϫ1 dissociation threshold energy. The elimination of ammonia is found to be substantially endothermic requiring 376 -380 kJ mol Ϫ1 at the dissociation threshold and depending on the dissociation pathway. The overall dissociation is slowed by the involvement of ion-molecule complexes along the dissociation pathways. The competing isomerization of 1 ؉ proceeds by a sequence of ring opening, internal rotations, imine flipping, ring closures, and proton migrations to effectively exchange the N-1 and N-10 atoms in 1 ؉ , so that either can be eliminated as ammonia. This mechanism explains the previous N-1/N-10 exchange upon collision-induced dissociation of protonated adenine. (J Am Soc Mass Spectrom 2005, 16, 1713-1726
The study of the holotype and of a new specimen of Nanchangosaurus suni (Reptilia; Diapsida; Hupehsuchia) revealed a suite of hitherto unrecognized characters. For example, Nanchangosaurus has bipartite neural spines and its vertebral count is nearly identical to that of Hupehsuchus. It differs from the latter in having poorly developed forelimbs despite the advanced ossification in the rest of the skeleton. Other differences all pertain to hupehsuchian plesiomorphies retained in Nanchangosaurus, such as low neural spines. The relationship of Hupehsuchia within Diapsida was analyzed based on a data matrix containing 41 taxa coded for 213 characters, of which 18 were identified as aquatic adaptations from functional inferences. These aquatic adaptations may be vulnerable to the argumentation of character homology because expectation for homoplasy is high. There is an apparent incongruence between phylogenetic signals from aquatic adaptations and the rest of the data, with aquatic adaptations favoring all marine reptiles but Helveticosaurus to form a super-clade. However, this super-clade does not obtain when aquatic adaptations were deleted, whereas individual marine reptile clades are all derived without them. We examined all possible combinations of the 18 aquatic adaptations (n = 262143) and found that four lineages of marine reptiles are recognized almost regardless of which of these features were included in the analysis: Hupehsuchia-Ichthyopterygia clade, Sauropterygia-Saurosphargidae clade, Thalattosauria, and Helveticosaurus. The interrelationships among these four depended on the combination of aquatic adaptations to be included, i.e., assumed to be homologous a priori by bypassing character argumentation. Hupehsuchia always appeared as the sister taxon of Ichthyopterygia.
Parahupehsuchus longus is a new species of marine reptile from the Lower Triassic of Yuan’an County, Hubei Province, China. It is unique among vertebrates for having a body wall that is completely surrounded by a bony tube, about 50 cm long and 6.5 cm deep, comprising overlapping ribs and gastralia. This tube and bony ossicles on the back are best interpreted as anti-predatory features, suggesting that there was predation pressure upon marine tetrapods in the Early Triassic. There is at least one sauropterygian that is sufficiently large to feed on Parahupehsuchus in the Nanzhang-Yuan’an fauna, together with six more species of potential prey marine reptiles with various degrees of body protection. Modern predators of marine tetrapods belong to the highest trophic levels in the marine ecosystem but such predators did not always exist through geologic time. The indication of marine-tetrapod feeding in the Nanzhang-Yuan’an fauna suggests that such a trophic level emerged for the first time in the Early Triassic. The recovery from the end-Permian extinction probably proceeded faster than traditionally thought for marine predators. Parahupehsuchus has superficially turtle-like features, namely expanded ribs without intercostal space, very short transverse processes, and a dorsal outgrowth from the neural spine. However, these features are structurally different from their turtle counterparts. Phylogeny suggests that they are convergent with the condition in turtles, which has a fundamentally different body plan that involves the folding of the body wall. Expanded ribs without intercostal space evolved at least twice and probably even more among reptiles.
Global climatic transitions and Tibetan Plateau uplifts are hypothesized to have profoundly impacted biodiversity in southeastern Asia. To further test the hypotheses related to the impacts of these incidents, we investigated the diversification patterns of the newt genus Tylototriton sensu lato, distributed across the mountain ranges of southeastern Asia. Gene-tree and species-tree analyses of two mitochondrial genes and two nuclear genes revealed five major clades in the genus, and suggested several cryptic species. Dating estimates suggested that the genus originated in the early-to-middle Miocene. Under different species delimitating scenarios, diversification analyses with birth-death likelihood tests indicated that the genus held a higher diversification rate in the late Miocene-to-Pliocene era than that in the Pleistocene. Ancestral area reconstructions indicated that the genus originated from the northern Indochina Peninsula. Accordingly, we hypothesized that the Miocene Climatic Transition triggered the diversification of the genus, and the reinforcement of East Asian monsoons associated with the stepwise uplifts of the Tibetan Plateau promoted the radiation of the genus in southeastern Asia during the Miocene-to-Pliocene period. Quaternary glacial cycles likely had limited effects on speciation events in the genus, but mainly had contributions on their intraspecific differentiations.
boundary and several excellent phylogenetic lineages of Baltoniodus, Trapezognathus, Periodon, and Microzarkodina are represented. The definition of the base of the Middle Ordovician is proposed to be the first appearance datum (FAD) of Baltoniodus? triangularis in the section. It is followed closely by the FAD of Microzarkodina flabellum, which is taken as a reasonable proxy for the boundary. This level approximates the boundary between the lower and upper intervals of the Azygograptus suecicus graptolite Biozone, and nearly coincides with the base of the Belonechitina henryi chitinozoan Biozone.The proposed GSSP for the base of the international Middle Ordovician Series is located in a roadside exposure at the base of Bed (SHod) 16, 10.57 m above the base of the Dawan Formation in the measured Huanghuachang section near Yichang City, southern China. The same faunal succession is also recorded from the Chenjiahe (formerly Daping) section, 5 km to the north of the Huanghuachang section. The proposed boundary horizon can be recognized and correlated globally with high precision in both relatively shallow-water carbonate facies as well as in deep-water graptolite facies. Zhen et al. (2003) recently revised P. aranda originally erected by Cooper (1981) and allocated the species into new genus Cooperignathus, resulting in some confusion with regard to the concept of this species. The recommended Huanghuachang section has excellent and well-known conodont, chitinozoan, graptolite, acritarch and other shelly fossil records in a stratigraphically continuous succession.
BackgroundIchthyosaurs were an important group of Mesozoic marine reptiles and existed from the Early Triassic to the early Late Cretaceous. Despite a great diversity in body shapes and feeding adaptations, all share greatly enlarged eyes, an elongated rostrum with numerous conical teeth, and a streamlined body.Methodology/Principal FindingsBased on new material from China and the restudy of Shastasaurus pacificus, we here reinterpret the classical large-bodied Late Triassic ichthyosaur genus Shastasaurus to differ greatly from the standard ichthyosaurian body plan, indicating much greater morphological diversity and range of feeding adaptations in ichthyosaurs than previously recognized. Phylogenetic analysis indicates a monophyletic clade consisting of the giant Shonisaurus sikanniensis, Guanlingsaurus liangae, and Shastasaurus pacificus to which the genus name Shastasaurus is applied. Shastasaurus liangae comb. nov. is from the Late Triassic (Carnian) Xiaowa Formation of Guizhou Province, southwestern China. The species combines a diminutive head with an entirely toothless and greatly reduced snout. The species also has by far the highest vertebral count among ichthyosaurs (86 presacral vertebrae and >110 caudal vertebrae), a count that is also very high for tetrapods in general. A reduced toothless snout and a diminutive head is also apparently present in the giant S. sikanniensis and presumably in S. pacificus.Conclusions/SignificanceIn analogy to many modern odontocetes, Shastasaurus is interpreted as a specialized suction feeder on unshelled cephalopods and fish, suggesting a unique but widespread Late Triassic diversification of toothless, suction-feeding ichthyosaurs. Suction feeding has not been hypothesized for any of the other diverse marine reptiles of the Mesozoic before, but in Shastasaurus may be linked to the Late Triassic minimum in atmospheric oxygen.
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