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Thermodynamic behavior of a phase transition in a model for sympatric speciation.

We investigate the macroscopic effects of the ingredients that drive the origin of species through sympatric speciation. In our model, sympatric speciation is obtained as we tune up the strength of competition between individuals with different phenotypes. As a function of this control parameter, we can characterize, through the behavior of a macroscopic order parameter, a phase transition from a nonspeciation to a speciation state of the system. The behavior of the first derivative of the order parameter with respect to the control parameter is consistent with a phase transition and exhibits a sharp peak at the transition point. For different resources distribution, the transition point is shifted, an effect similar to pressure in a PVT system. The inverse of the parameter related to a sexual selection strength behaves like an external field in the system and, as thus, is also a control parameter. The macroscopic effects of the biological parameters used in our model are a reminiscent of the behavior of thermodynamic quantities in a phase transition of an equilibrium physical system.

Biological Evolution↗

Phylogenomic evidence provides insights into the phylogeny and speciation patterns in the subgenus Caloscordum (Allium, Amaryllidaceae).

Phylogenomics with abundant informative sites offers a powerful means for elucidating complex diversification history. Here, we collected 22 samples from 18 populations representing all species of subgenus Caloscordum (Allium). Using transcriptome and whole-genome resequencing data, we generated 1755 low-copy nuclear genes and 81 plastid genes. By integrating morphological and phylogenomic evidence, we clarified the subgenus's complex evolutionary histories and speciation patterns. A total of 18 morphological characteristics were analysed, with a taxonomic framework established. Our analyses resolved robust species relationships despite detecting extensive phylogenetic discordances, which were attributed to incomplete lineage sorting (ILS) and hybridization. Specifically, our results suggest that A. inutile originated via rapid budding speciation from the widespread A. tubiflorum. This process likely coincided with mid-Pleistocene glacial-interglacial cycles and may have been reinforced by geographic isolation and ecological adaptation. In contrast, the sole tetraploid species, A. peikingense, was confirmed to be of hybrid origin, derived from A. neriniflorum and A. tubiflorum. This allopolyploidization event appears to have been facilitated by secondary contact between the parent species, which was likely associated with climatic oscillations within the 35° N-45° N arid belt. Overall, our findings elucidate the intricate speciation patterns within Caloscordum and highlight how the interplay of polyploidization, ecological isolation, and tectonic uplift-driven aridification has shaped plant diversity in East Asia.

Phylogeny↗

Aplf/Dna2 variants drive chromosomal fission and accelerate speciation in zokors.

Chromosomal fissions and fusions are common, yet the molecular mechanisms and implications in speciation remain poorly understood. Here, we confirm a fission event in one zokor species through multiple-omics and functional analyses. We traced this event to a mutation in a splicing enhancer of the DNA repair gene Aplf in the fission-bearing species, which caused exon skipping and produced a truncated protein that disrupted DNA repair. An intronic deletion in Dna2, known to facilitate neo-telomere formation when knocked out, reduced gene activity. These variants collectively drove chromosomal fission in this zokor species. The newly formed chromosome became fixed due to carrying essential genes and strong selective pressure. While geographic isolation likely initiated the divergence of this species and the sister one, the fission event and associated decline at the chromosome level in gene flow probably exacerbated the speciation process. Our work elucidates the genetic basis of chromosomal fission and underscores its role in speciation dynamics.

Multiomics↗

Homoploid hybrid speciation in an extreme habitat.

According to theory, homoploid hybrid speciation, which is hybrid speciation without a change in chromosome number, is facilitated by adaptation to a novel or extreme habitat. Using molecular and ecological data, we found that the alpine-adapted butterflies in the genus Lycaeides are the product of hybrid speciation. The alpine populations possess a mosaic genome derived from both L. melissa and L. idas and are differentiated from and younger than their putative parental species. As predicted, adaptive traits may allow for persistence in the environmentally extreme alpine habitat and reproductively isolate these populations from their parental species.

Adaptation, Physiological↗

Rapid identification and speciation of Haemophilus bacteria by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

Several species of the genus Haemophilus are well known etiological agents of pneumonia, meningitis, conjunctivitis, epiglottitis and chancroid. However, identification and speciation of Haemophilus is both time consuming and labor intensive. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI/TOF-MS) has been used by several investigators to profile proteins from intact and disrupted bacteria; consequently, MALDI/TOF-MS has emerged as a powerful tool in diagnostic bacteriology. This paper reports the use of MALDI/TOF-MS as a technique for the rapid identification and speciation of Haemophilus. This technique was used to not only identify the pathogen, H. ducreyi, but also to determine strain differences from different isolates. Mass spectral 'fingerprints' were obtained which permitted the rapid speciation of not only pathogenic forms of Haemophilus, but also those bacteria which are normally regarded as non-pathogenic and members of the normal flora. MALDI/TOF mass spectra can be acquired in 10 min, allowing the identification of Haemophilus spp. within 24 h rather than the 48 h or more needed for traditional bacteriological methods. In addition, these are the first mass spectral fingerprints available in the literature for many of these organisms.

Aggregatibacter actinomycetemcomitans↗

On-line hyphenation of capillary electrophoresis with flame-heated furnace atomic absorption spectrometry for trace mercury speciation.

Capillary electrophoresis (CE) was directly interfaced to flame-heated furnace atomic absorption spectrometry (FHF-AAS) via a laboratory-made thermospray interface for nanoliter trace element speciation. The CE-FHF-AAS interface integrated the superiorities of stable CE separation, complete sample introduction, and continuous vaporization for AAS detection without the need of extra external heat sources and any post-column derivation steps. To demonstrate the usefulness of the developed hybrid technique for speciation analysis, three environmentally significant and toxic forms of methylmercury (MeHg), phenylmercury (PhHg), and inorganic mercury (Hg(II)) were taken as model analytes. Baseline separation of the three mercury species was achieved by CE in a 60 cm long x 75 microm inner diameter fused-silica capillary at 20 kV and using a mixture of 100 mM boric acid and 10% v/v methanol (pH 8.30) as running electrolyte. The precision (relative standard deviation, RSD, n = 7) of migration time, peak area and peak height for the mercury species at 500 microg x L(-1) (as Hg) level were in the range of 0.9-1.2%, 1.5-1.9%, and 1.4-2.0%, respectively. The detection limit (S/N = 3) of three mercury species was 3.0 +/- 0.15 pg (as Hg), corresponding to 50.8 +/- 2.4 microg x L(-1) (as Hg) for 60 nL sample injection, which was almost independent on specific mercury species. The developed hybrid technique was successfully applied to the speciation analysis of mercury in a certified reference material (DORM-2, dogfish muscle).

Electrophoresis, Capillary↗

Speciation of selenium compounds by open tubular capillary electrochromatography-inductively coupled plasma mass spectrometry.

We introduce a T-type interface and a crossflow nebulizer to find ways to combine CEC with inductively coupled plasma MS (ICP-MS) detection for selenium speciation. For CEC separation, we employed a macrocyclic polyamine-bonded phase capillary as the separation column and a bare fused-silica capillary filled with the make-up liquid (0.05 M HNO3). The effect of nebulizer gas flow rate, make-up liquid flow, type, concentration and pH of the mobile phase on the separation have been studied. Tris buffer of 50 mM at pH 8.50 gave the best performance for selenium speciation. The reproducibility of the retention time indicated that sample injection by electrokinetic and nebulizer gas flow was better than that by self-aspiration alone. The detection limits for selenate, selenite, selenocystine and selenomethionine were found to be 2.40, 3.53, 12.86 and 11.25 ng/mL, respectively. Due to the high sensitivity and element-specific detection, as well as the high selectivity of the bonded phase, quantitative analysis of selenium speciation in urine was also achieved.

Buffers↗

Speciation of nitrogen-containing compounds in diesel fuel by comprehensive two-dimensional gas chromatography.

Nitrogen-containing compounds in diesel fuel have been speciated by comprehensive two-dimensional gas chromatography with nitrogen chemiluminescence detector (GC x GC-NCD). The speciation of nitrogen-containing compounds in diesel is difficult because of low concentration and complexity. The advantages of GC x GC are improved resolution and enhanced sensitivity. GC x GC-NCD can achieve the type and class separation of nitrogen-containing compounds with an appropriate separation column combination. Diesel contains both neutral (indoles and carbazoles) and basic (pyridines and quinolines) nitrogen-containing compounds. Relative concentrations of each class as well as each carbon number family can be quantified by integrating their peak volumes. This study demonstrates the capability of GC x GC-NCD for speciation of nitrogen-containing compound classes.

Journal Article↗

Inductively coupled plasma mass spectrometry in separation techniques: recent trends in phosphorus speciation.

Inductively coupled plasma-MS (ICP-MS) and its combined use with molecular mass spectrometric techniques have become the most promising detection techniques in speciation studies. High sensitivity and element specificity of ICP-MS has the advantage of detecting trace amounts of the species of interest in complex matrices. This review is divided into two parts. In the first part, suitable use of ICP-MS either online or offline with currently used separation techniques such as HPLC, CE, and gel electrophoresis in speciation analysis is briefly discussed. In the second part, recent applications (1999-2005) of phosphorus speciation is presented to elucidate the importance of ICP-MS in separation methods and to illustrate its importance in nonmetal detection.

Chromatography, Liquid↗

Speciation and quantitation of underivatized and Ellman's derivatized biological thiols and disulfides by capillary electrophoresis.

Capillary electrophoresis (CE) methods have been developed for the speciation and quantitation of thiols and disulfides of biological interest, including the endogenous compounds glutathione, glutathione disulfide, cysteine, cystine, homocysteine, and homocystine and the therapeutic agents penicillamine, penicillamine disulfide, N-acetylcysteine, and captopril. Good speciation and quantitation were achieved for the underivatized thiols and disulfides using a detection wavelength of 200 nm; detection limits were in the range 20-90 microM (1-4 pmol) using a 50-microns-diameter capillary. To achieve lower detection limits, thiols were derivatized with the thiol-specific probe molecule, 5,5'-dithio-bis-(2-nitrobenzoic acid) (Ellman's reagent). Good speciation and quantitation were achieved for the Ellman's derivatized thiols using a detection wavelength of 357 nm; detection limits were in the range 5-50 microM (0.03-0.3 pmol) using a 25-microns-diameter capillary. Both the underivatized and derivatized methods were applied to the determination of glutathione in human erythrocytes. Glutathione concentrations of 2-3 mM were obtained for the erythrocyte samples analyzed, with good agreement between results obtained by the two methods.

Captopril↗

The influence of mucus on copper speciation in the gill microenvironment of carp (Cyprinus carpio).

pH and mucus (as total organic carbon) in the gill microenvironment of carp, Cyprinus carpio, exposed to various concentrations of total copper were measured in an exposure experiment using Playle's apparatus. The activities of free copper ions in both inspired and expired waters were determined using a copper ion selective electrode. A trial-and-error procedure of coupling species distribution calculations (MINEQA2) with single-site complexation modeling (mucus-copper) was proposed for computation of both copper speciation and complexation capacity of gill mucus for copper in an interactive loop. The method was demonstrated to be valid in calculating the metal speciation in this study. It was found that pH and alkalinity in the gill microenvironment were slightly higher than in the surrounding water of pH 6.7. The rates of excretion of CO(2), HCO(-)(3), and mucus at the gills increased, either linearly or nonlinearly with increases in the total copper concentration in the surrounding water. The conditional complexation stability constant of the mucus was calculated as log k=5.32, while the complexation stability equivalent concentration of the mucus was derived as 0.95 mmolCu/mgC. As a consequence of changes in pH and alkalinity, in conjunction with occurrence of mucus, copper speciation in the gill microenvironment is significantly different from that in the surrounding water, with 3-20% of the copper complexed by the gill mucus. The sequence of species domination also shifted from CuCO(0)(3), Cu(2+), CuHCO(+)(3), and Cu(OH)(0)(2) in the surrounding water to CuCO(0)(3), Cu(2+), Cu(OH)(0)(2), CuHCO(+)(3), and mucus-Cu in the gill microenvironment.

Animals↗

Phylogeny and evolution of the Sulidae (Aves:Pelecaniformes): a test of alternative modes of speciation.

Although the allopatric model of speciation is widely accepted, it does not provide a satisfactory explanation for many evolutionary phenomena. Several alternative models exist, but they remain largely untested for vertebrate animals. In the present paper, a molecular phylogeny was used to test competing models of speciation in a seabird family, the Sulidae. A segment including 807 base pairs of the mitochondrial cytochrome b gene was sequenced from all extant sulid species, and phylogenetic methods were used to test model-specific predictions regarding tree topologies, distributions of sister taxa, timing of vicariant events, and comparative biology. Both the neighbor-joining and parsimony analyses placed sequences of gannets (Morus spp.) and boobies of the genus Sula in separate, monophyletic lineages. Sequences of Cape (M. capensis) and Australasian (M. serrator) gannets clustered together, and the sequence of Abbott's booby (Papasula abbotti) was basal to those of the gannets. Sequences of blue-footed (S. nebouxii) and Peruvian (S. variegata) boobies were sisters and formed a monophyletic group with the masked booby (S. dactylatra). The red-footed booby (S. sula) sequence was the most divergent of the Sula boobies. All relationships received strong support from standard-error tests and bootstrap analysis. Substitution rates were similar to those suggested for mammals and suggested that most lineages arose within the last 3 million years. Lineage divergence events for which the mode of speciation could be deduced did not fit the predictions of either allopatric or sympatric models, but apparently involved either peripatric or parapatric processes.

Animals↗

Change of speciation of Cu(II) in growth medium due to uptake of ammonia by Pseudomonas testosteroni during growth.

Growth of Pseudomonas testosteroni in a medium containing 1 mM Cu(II) causes a color change from blue to green. The spectrum of the supernatant solution from the blue culture shows an absorption at 660 nm, identical to that of 1 mM [Cu(II)] in the medium. The green supernatant solution shows a UV absorption, which tails into the visible and so is responsible for the green color, and a d-d absorption at 720 nm. The absorption at 660 nm for the blue supernatant solution is probably due to [Cu(NH3)3(H2O)3]2+. Growth of the organism causes loss of ammonia and a speciation change to [CU(NH3)2(H2O)4]2+, with a shift in absorption maximum from 660 to 720 nm. These conclusions are based upon the spectra of known aquaammine complexes of Cu(II) and calculations of the speciation of Cu(II) before and after growth. Change in metal speciation owing to nutrient uptake by an organism does not appear to have been recognized previously.

Ammonia↗

Accuracy and traceability concepts applied to environmental speciation analysis.

Traceability issues are of increasing concern in all fields where chemical measurements form the basis for decisions. The concepts of accuracy and traceability as applied to environmental analysis are, however, still prone to misunderstandings, which has been recently illustrated by controversial discussions among the analytical community with respect to accuracy and traceability issues in the area of speciation analysis. Analytical techniques used for the determination of chemical species (speciation analysis) are generally based on a succession of steps (e.g. extraction derivatisation, separation, detection) which are all prone to various sources of systematic errors. Many speciation measurement techniques have been studied within the last decade through interlaboratory studies and certification of reference materials. These collaborative efforts have been understood as being directed towards strive for accuracy (trueness and precision). It has been recognised recently that the achievements actually enabled mostly to establish reference points (e.g. certified values in reference materials) which does not necessarily correspond to 'true values' but rather offer a mean for laboratories to compare their data internationally and, hence, achieve traceability. This ambiguity still generates confusion and misunderstandings among the scientific community. This communication discusses this issue, focusing on analytical measurements only. Extending discussions on general traceability issues would imply an examination of steps prior to laboratory work (sampling, storage, etc.) which is beyond the scope of this contribution.

Chemistry Techniques, Analytical↗

Speciation of chromium in plasma and liver tissue of endstage renal failure patients on continuous ambulatory peritoneal dialysis.

This work is a first attempt to determine the speciation of Cr in human plasma. With the aid of in vitro and in vivo 51Cr-labeled experiments, it was possible to develop the necessary biochemical techniques for the separation of the plasma proteins. Further work will use real samples, taking care to avoid contamination of the various fractions and to preserve the original binding of the Cr to the specific plasma compounds. In a first attempt on the distribution of Cr over the different organelles of liver tissue, work will be restricted to in vivo labeled experiments with rats. The procedure to do the speciation work seems so elaborate that it may be impossible ever to achieve the contemplated speciation of Cr in human liver tissue by subcellular fractionation.

Adult↗

Phylogeny and rapid northern and southern hemisphere speciation of goldfinches during the Miocene and Pliocene epochs.

Mitochondrial cytochrome b (cyt b) from 25 out of 31 extant goldfinches, siskins, greenfinches and redpolls (genus Carduelis) has been sequenced from living samples taken around the world, specimens have also been photographed. Phylogenetic analysis consistently gave the same groups of birds, and this grouping was generally related to geographical proximity. It has been supposed that Pleistocene glaciations played a crucial role in the origin of extant diversity and distribution of Northern Hemisphere vertebrates. Molecular comparison of most extant songbird species belonging to the genus Carduelis does not support this assertion. The fossil record of chicken and pheasant divergence time has been used to calibrate the molecular clock; cyt b DNA dendrograms suggest that speciation in Carduelinae birds occurred during the Miocene and Pliocene Epochs (9-2 million years ago) in both the Northern and Southern Hemispheres. Only about 4% average amount of nucleotide substitution per lineage is found between the most distant Carduelis species; this suggests a remarkably rapid radiation when compared with the radiation of other passerine songbird genera. In addition, a continuum of small songbird speciation may be found during the Miocene Epoch in parallel with speciation of other orders (i.e. Galliformes, chicken/pheasant). Pleistocene glaciations may have been important in subspeciation (i.e. Eastern European grey-headed goldfinches/Western European black-headed goldfinches) and also in ice-induced vicariance (isolation) (i.e. siskin in Western Europe vs. siskin in Far East Asia) around the world. European isolated Serinus citrinella (citril finch) is not a canary, but a true goldfinch. South American siskins have quickly radiated in the last 4 million years coinciding with the emergence of the Isthmus of Panama; probably, a North American siskin related to C. notata invaded a suitable and varied biotope (the South American island) for Carduelis birds. North American goldfinches may be renamed as siskins, because they have a distant genetic relationship with European goldfinches. Genus Acanthis could be dropped, and thus redpolls should be separated from twite and linnet, the latter (Europeans) probably being related to American goldfinches. Also, reproductive barriers are observed between closely related species and not between other more distant ones. Finally, a tentative classification for genus Carduelis species is suggested.

Animals↗

HPLC-ICP-MS determination of selenium distribution and speciation in different types of nut.

In addition to determination of total selenium in nuts, the element distribution among different fractions (lipid extract, low molecular weight, and protein fractions), and speciation analysis were studied. Improved precision for total selenium determination was observed after elimination of lipids. Because selenium was not detected in any of the lipid extracts obtained from the different types of nuts (ICP-MS), in each determination and/or speciation procedure used in this work lipids were extracted (chloroform-methanol, 2:1) and discarded before analysis. In agreement with previously reported data, high selenium levels were found in Brazil nuts (those purchased without shells contained approximately a quarter the content than those purchased with shells) and significantly lower levels in walnuts, cashews, and pecans nuts. Low-molecular-weight compounds were extracted with perchloric acid (0.4 mol L(-1)) to furnish a fraction containing 3 to 15% of the total selenium in different types of nuts. The proteins were isolated from nut samples by dissolution in 0.1 mol L(-1) sodium hydroxide and subsequent precipitation with acetone. They were then dissolved in phosphate buffer pH 7.5. Analysis of protein fractions focused on selenium in two possible states - weakly and firmly bound to proteins. Results obtained for Brazil nuts by size-exclusion chromatography with on-line ICP-MS detection, in the absence and in the presence of beta-mercaptoethanol, showed that approximately 12% of total selenium was weakly bound to proteins. To obtain information about firmly bound selenium, the protein extracts were hydrolyzed enzymatically with proteinase K. Speciation was performed by means of ion-pairing HPLC-ICP-MS. The primary species found in all types of nuts was Se-methionine (19-25% of total selenium for different types of nuts).

Chromatography, High Pressure Liquid↗

Electrochemical vapor generation of selenium species after online photolysis and reduction by UV-irradiation under nano TiO2 photocatalysis and its application to selenium speciation by HPLC coupled with atomic fluorescence spectrometry.

An online UV photolysis and UV/TiO2 photocatalysis reduction device (UV-UV/TiO2 PCRD) and an electrochemical vapor generation (ECVG) cell have been used for the first time as an interface between high-performance liquid chromatography (HPLC) and atomic fluorescence spectrometry (AFS) for selenium speciation. The newly designed ECVG cell of approximately 115 microL dead volume consists of a carbon fiber cathode and a platinum loop anode; the atomic hydrogen generated on the cathode was used to reduce selenium to vapor species for AFS determination. The noise was greatly reduced compared with that obtained by use of the UV-UV/TiO2 PCRD-KBH4-acid interface. The detection limits obtained for seleno-DL: -cystine (SeCys), selenite (Se(IV)), seleno-DL: -methionine (SeMet), and selenate (Se(VI)) were 2.1, 2.9, 4.3, and 3.5 ng mL(-1), respectively. The proposed method was successfully applied to the speciation of selenium in water-soluble extracts of garlic shoots cultured with different selenium species. The results obtained suggested that UV-UV/TiO2 PCRD-ECVG should be an effective interface between HPLC and AFS for the speciation of elements amenable to vapor generation, and is superior to methods involving KBH4.

Catalysis↗