Microgeographic speciation in a complex of Anatolian bush crickets facilitated by fast evolution of reproductive isolation.

Identifying the drivers of microgeographic speciation (i.e., speciation over small, local geographic scales) is key to understand the origin of speciose groups. Here, we use genomic data to infer the demographic processes underlying diversification in Poecilimon luschani (Orthoptera: Tettigoniidae), a species complex belonging to the most diverse genus of bush crickets from the Mediterranean region (>170 taxa) that comprises three recognized subspecies with small allopatric distributions in the topographically complex Teke Peninsula, southwestern Anatolia. Phylogenomic reconstructions that include all other taxa within the species group confirmed that subspecies of P. luschani originated from a common ancestor during the Pleistocene, supporting recent (<1 Ma) diversification within a small geographical area (ca. 120 × 80 km). Genetic clustering analyses corroborated the distinctiveness of each subspecies and the cohesiveness of their respective populations, with abrupt genetic discontinuities coinciding with contemporary range boundaries. Indeed, our analyses uncovered the presence of two sympatric cryptic sister lineages that diverged <300 ka ago and do not admix despite being co-distributed. Collectively, these results support that all lineages within the complex represent independently evolving entities corresponding to full-fledged species. Statistical evaluation of alternative models of speciation strongly supports a scenario of divergence in isolation followed by a period of limited gene flow during the last glacial period, when all lineages experienced marked expansions according to demographic reconstructions. Our study exemplifies how localized allopatric divergence and fast evolution of reproductive isolation can promote microgeographic speciation and explain the high rates of endemism characterizing biodiversity hotspots.

Genome-wide screening for selection signatures in native and cosmopolitan cattle breeds reared in Türkiye.

Via long-term natural and artificial selection pressure, homozygosity may extend across the genome, leaving genomic patterns called selection signatures. This study is the first attempt to assess genome-wide selection signatures in six native Turkish and two cosmopolitan cattle breeds by 211.119 bi-allelic SNPs recovered using the double digest restriction associated DNA sequencing method. The integrated haplotype score (iHS) statistic was utilised to reveal selection signatures within populations, whereas the cross-population extended haplotype homozygosity (XP-EHH) and fixation index (FST ) approaches were preferred to reveal differently fixed genomic regions between native Turkish and cosmopolitan cattle breeds. Selection signatures in 142 genomic regions containing 305 genes were detected within eight cattle breeds by iHS statistics. The XP-EHH and FST approaches revealed that 197 and 114 SNPs were under selection pressure, respectively, which overlapped with 144 and 190 genes, respectively. A total of 18 genes were detected by at least two approaches. Six genes related to disease resistance (TTP2), meat yield (DIAPH3 and METTL21C), meat quality (ZNF24 and ZNF397) and first calving interval (ZSCAN30) turned out to be differently fixed between native Turkish and cosmopolitan cattle breeds, as they were identified by both XP-EHH and FST approaches. In addition, the iHS approach revealed that eight genes associated with visual modality (LSGN), olfaction (MOXD2, OR4C1F and OR4C1F), and immune response (TRBV3-1 and CLDN10) were under selection pressure in both native and cosmopolitan cattle breeds. Owing to their being significantly related to survival traits, these regions may have played a key role in cattle genome evolution. Future studies utilising denser genetic data are required to obtain deeper knowledge on effects of natural and artificial selection in Anatolian cattle breeds. © 2023 Stichting International Foundation for Animal Genetics.

Genome-wide genetic variation and population structure of native and cosmopolitan cattle breeds reared in Türkiye.

This is the first comprehensive study to reveal genetic variation and population structure at genome level in six Anatolian (Anatolian Black, East Anatolian Red, South Anatolian Red, South Anatolian Yellow, Turkish Grey Steppe, and Zavot) and two cosmopolitan (Brown Swiss and Holstein Friesian) cattle breeds reared in Türkiye. Being 20 samples from each population, a total of 160 blood samples retrieved from representative herds were utilized to generate genomic libraries by ddRADseq method. Genomic libraries sequenced by Illumina HiSeq X Ten instrument revealed a total of 211,119 bi-allelic SNPs with high call rate. Compared to cosmopolitan cattle breeds, a higher genetic variation was observed in native Turkish cattle with an average of 0.380 observed heterozygosity. Genetic distances were comparatively low between native cattle breeds, whereas the highest genetic distance (0.064) was detected between South Anatolian Yellow and Brown Swiss. Population structure analyses showed that the native Turkish and cosmopolitan cattle breeds were clearly different from each other according to their phylogenetic origin. Besides, a high level of genetic admixture was detected among Anatolian Black, Turkish Grey Steppe, South Anatolian Red, and South Anatolian Yellow, whereas East Anatolian Red and Zavot were distinct from the other native and cosmopolitan cattle breeds. TreeMix algorithm under the assumption of one and two migration events revealed a migration route from Anatolian clade to Anatolian Black, while a second migration edge was drawn from Brown Swiss to East Anatolian Red. This study demonstrates the importance of national conservation studies in the native breeds whose population size has dramatically decreased. In addition, SNP arrays and next-generation sequencing platforms are recommended for future studies to reveal the genetic variation of other local Turkish livestock species to arrange effective conservation programs.

HIPPIE: a new platform for ambient-pressure X-ray photoelectron spectroscopy at the MAX IV Laboratory.

HIPPIE is a soft X-ray beamline on the 3 GeV electron storage ring of the MAX IV Laboratory, equipped with a novel ambient-pressure X-ray photoelectron spectroscopy (APXPS) instrument. The endstation is dedicated to performing in situ and operando X-ray photoelectron spectroscopy experiments in the presence of a controlled gaseous atmosphere at pressures up to 30 mbar [1 mbar = 100 Pa] as well as under ultra-high-vacuum conditions. The photon energy range is 250 to 2200 eV in planar polarization and with photon fluxes >1012 photons s-1 (500 mA ring current) at a resolving power of greater than 10000 and up to a maximum of 32000. The endstation currently provides two sample environments: a catalysis cell and an electrochemical/liquid cell. The former allows APXPS measurements of solid samples in the presence of a gaseous atmosphere (with a mixture of up to eight gases and a vapour of a liquid) and simultaneous analysis of the inlet/outlet gas composition by online mass spectrometry. The latter is a more versatile setup primarily designed for APXPS at the solid-liquid (dip-and-pull setup) or liquid-gas (liquid microjet) interfaces under full electrochemical control, and it can also be used as an open port for ad hoc-designed non-standard APXPS experiments with different sample environments. The catalysis cell can be further equipped with an IR reflection-absorption spectrometer, allowing for simultaneous APXPS and IR spectroscopy of the samples. The endstation is set up to easily accommodate further sample environments.

Direct observation of the dealloying process of a platinum-yttrium nanoparticle fuel cell cathode and its oxygenated species during the oxygen reduction reaction.

Size-selected 9 nm PtxY nanoparticles have recently shown an outstanding catalytic activity for the oxygen reduction reaction, representing a promising cathode catalyst for proton exchange membrane fuel cells (PEMFCs). Studying their electrochemical dealloying is a fundamental step towards the understanding of both their activity and stability. Herein, size-selected 9 nm PtxY nanoparticles have been deposited on the cathode side of a PEMFC specifically designed for in situ ambient pressure X-ray photoelectron spectroscopy (APXPS). The dealloying mechanism was followed in situ for the first time. It proceeds through the progressive oxidation of alloyed Y atoms, soon leading to the accumulation of Y(3+) cations at the cathode. Acid leaching with sulfuric acid is capable of accelerating the dealloying process and removing these Y(3+) cations which might cause long term degradation of the membrane. The use of APXPS under near operating conditions allowed observing the population of oxygenated surface species as a function of the electrochemical potential. Similar to the case of pure Pt nanoparticles, non-hydrated hydroxide plays a key role in the ORR catalytic process.

Different reactivity of the various platinum oxides and chemisorbed oxygen in CO oxidation on Pt(111).

We have used X-ray photoelectron spectroscopy and polarization-resolved O K-edge X-ray absorption spectroscopy to investigate the reactivity of various oxygen covered Pt(111) surfaces, which emerge under high temperature and pressure conditions, toward CO. We find that the reactivity of the O/Pt(111) system decreases monotonically with increasing oxygen coverage. Of the three surface oxygen phases, viz., chemisorbed oxygen (O(ad)), a PtO-like surface oxide, and α-PtO2 trilayers, Oad exhibits the highest reactivity toward CO, whereas α-PtO2 trilayers exhibit the lowest. Pt(111) surfaces fully terminated by α-PtO2 trilayers are inert to CO. Here it is proposed that the reactive phase is either O(ad) or PtO-like surface oxide phase on bare non-CO poisoned Pt regions with PtO2 as majority spectator species.

Comparison of x-ray absorption spectra between water and ice: new ice data with low pre-edge absorption cross-section.

The effect of crystal growth conditions on the O K-edge x-ray absorption spectra of ice is investigated through detailed analysis of the spectral features. The amount of ice defects is found to be minimized on hydrophobic surfaces, such as BaF2(111), with low concentration of nucleation centers. This is manifested through a reduction of the absorption cross-section at 535 eV, which is associated with distorted hydrogen bonds. Furthermore, a connection is made between the observed increase in spectral intensity between 544 and 548 eV and high-symmetry points in the electronic band structure, suggesting a more extended hydrogen-bond network as compared to ices prepared differently. The spectral differences for various ice preparations are compared to the temperature dependence of spectra of liquid water upon supercooling. A double-peak feature in the absorption cross-section between 540 and 543 eV is identified as a characteristic of the crystalline phase. The connection to the interpretation of the liquid phase O K-edge x-ray absorption spectrum is extensively discussed.

In†situ observation of surface species on iridium oxide nanoparticles during the oxygen evolution reaction.

An iridium oxide nanoparticle electrocatalyst under oxygen evolution reaction conditions was probed in situ by ambient-pressure X-ray photoelectron spectroscopy. Under OER conditions, iridium undergoes a change in oxidation state from Ir(IV) to Ir(V) that takes place predominantly at the surface of the catalyst. The chemical change in iridium is coupled to a decrease in surface hydroxide, providing experimental evidence which strongly suggests that the oxygen evolution reaction on iridium oxide occurs through an OOH-mediated deprotonation mechanism.

ALD-Engineered CuxO Overlayers Transform ZnO Nanorods for Selective Production of CO in Electrochemical CO2 Reduction.

The electrochemical CO2 reduction reaction (CO2RR) holds tremendous promise as a strategy for lowering atmospheric CO2 levels and creating new clean energy sources. The conversion of CO2RR to CO, in particular, has garnered significant scientific interest due to its industrial feasibility. Within this context, the CuZn-based electrocatalyst presents an attractive alternative to conventional CO-selective electrocatalysts, which are often costly and scarce. Nevertheless, the wide-range utilization of CuZn electrocatalysts requires a more comprehensive understanding of their performance and characteristics. In this study, we synthesized ZnO nanorods through electrodeposition and subsequently coated them with CuxO overlayers prepared by atomic layer deposition (ALD). CuxO significantly enhanced CO selectivity, and 88% CO selectivity at a relatively low potential of -0.8 V was obtained on an optimized CuxO overlayer thickness (CuxO-250/ZnO). The addition of CuxO on ZnO was found to dramatically increase the electrochemical surface area (ESCA), lower the charge-transfer resistance (Rct), and introduce new active sites in the ε-CuZn4 phase. Furthermore, electrochemical Raman spectroscopy results showed that the CuxO-250/ALD electrode developed a ZnO layer on the surface during the CO2RR, while the bare ZnO electrode showed no evidence of ZnO during the reaction. These results suggest that the addition of CuxO by ALD played a crucial role in stabilizing ZnO on the surface. The initial amount of CuxO was shown to further affect the redeposition of the ZnO layer and hence affect the final composition of the surface. We attribute the improvement in CO selectivity to the introduction of both ε-CuZn4 and ZnO that developed during the CO2RR. Overall, our study provides new insights into the dynamic behavior and surface composition of CuZn electrocatalysts during CO2RR.

Interlayer carbon bond formation induced by hydrogen adsorption in few-layer supported graphene.

We report on the hydrogen adsorption induced phase transition of a few layer graphene (1 to 4 layers) to a diamondlike structure on Pt(111) based on core level x-ray spectroscopy, temperature programed desorption, infrared spectroscopy, and density functional theory total energy calculations. The surface adsorption of hydrogen induces a hybridization change of carbon from the sp2 to the sp3 bond symmetry, which propagates through the graphene layers, resulting in interlayer carbon bond formation. The structure is stabilized through the termination of interfacial sp3 carbon atoms by the substrate. The structural transformation occurs as a consequence of high adsorption energy.

Psorodonotus venosus group (Orthoptera, Tettigoniidae; Tettigoniinae): geometric morphometry revealed two new species in the group.

Psorodonotus (Orthoptera, Tettigoniidae) includes 11 species distributed in Caucasus, Anatolia and Balkans. Although its present taxonomy is problematic, mainly three species groups can be distinguished; (i) The Specularis Group, (ii) The Caucasicus Group and (iii) The Venosus Group. Our recent studies on the genus have revealed presence of two new species in the last species group. Morphology of the species group studied both qualitatively and quantitatively using linear metric data of pronotum, tegmina and hind femur, and geometric data of male cerci and ovipositor. Morphological data were accompanied by data obtained from male calling song. Morphological and song data were produced from six different populations from North and Eastern part of Turkey: (1) Hakkari, (2) Tendürek, (3) Giresun, (4) Artvin, (5) Kars and (6) Agri. Qualitative and quantitative morphology, either linear-metric or geometric, suggest last three population as members of the same unit, but each of other three as different units. Song data are also largely in support of the morphological results. Necessary illustrations were provided to document results visually. Following conclusions were made: (1) the Artvin, Kars and Agri populations represent typical P. venosus and the Giresun population P. rugulosus, (2) each of the Hakkari and Tendürek populations represents a new species and P. hakkari sp. n. and P. tendurek sp. n. described by comparing with other members of P. venosus group, (3) P. rugulosus, P. hakkari sp. n. and P. tendurek sp. n. differ from P. venosus mainly by the longer cerci (extend to or beyond end of abdomen) and indistinct tubercles on surface of pronotal disc in female. P. rugulosus and P. tendurek sp. n. are also similar by sharing presence of two loud elements in a syllable (one in P. venosus, song of P. hakkari sp. n. is not available). But, similarities in phenotype are in conflict with relationships suggested by genetic data. 

Geographic Genetic Structure of Alectoris chukar in Türkiye: Post-LGM-Induced Hybridization and Human-Mediated Contaminations.

Türkiye is considered an important evolutionary area for Chukar partridge (Alectoris chukar), since it is both a potential ancestral area and a diversification center for the species. Using 2 mitochondrial (Cty-b and D-loop) and 13 polymorphic microsatellite markers, we investigated the geographic genetic structure of A. chukar populations to determine how past climatic fluctuations and human activities have shaped the gene pool of this species in Türkiye. Our results indicate, firstly, that only A. chukar of the genus Alectoris is present in Türkiye (Anatolia and Thrace), with no natural or artificial gene flow from congenerics. Secondly, the geographic genetic structure of the species in Türkiye has been shaped by topographic heterogeneity, Pleistocene climatic fluctuations, and artificial transport by humans. Third, there appears to be three genetic clusters: Thracian, Eastern, and Western. Fourth, the post-LGM demographic expansion of the Eastern and Western populations has formed a hybrid zone in Central Anatolia (~8 kyBP). Fifth, the rate of China clade-B contamination in Türkiye is about 8% in mtDNA and about 12% in nuDNA, with the Southeastern Anatolian population having the highest contamination. Sixth, the Thracian population was the most genetically distinct, with the lowest genetic diversity and highest level of inbreeding and no China clad-B contamination. These results can contribute to the conservation regarding A. chukar populations, especially the Thracian population.

Single-Atom Sn-Loaded Exfoliated Layered Titanate Revealing Enhanced Photocatalytic Activity in Hydrogen Generation.

Green H2 generation through layered materials plays a significant role among a wide variety of materials owing to their high theoretical surface area and distinctive features in (photo)catalysis. Layered titanates (LTs) are a class of these materials, but they suffer from large bandgaps and a layers' stacked form. We first address the successful exfoliation of bulk LT to exfoliated few-layer sheets via long-term dilute HCl treatment at room temperature without any organic exfoliating agents. Then, we demonstrate a substantial photocatalytic activity enhancement through the loading of Sn single atoms on exfoliated LTs (K0.8Ti1.73Li0.27O4). Comprehensive analysis, including time-resolved photoluminescence spectroscopy, revealed the modification of electronic and physical properties of the exfoliated layered titanate for better solar photocatalysis. Upon treating the exfoliated titanate in SnCl2 solution, a Sn single atom was successfully loaded on the exfoliated titanate, which was characterized by spectroscopic and microscopic techniques, including aberration-corrected transmission electron microscopy. The exfoliated titanate with an optimal Sn loading exhibited a good photocatalytic H2 evolution from water containing methanol and from ammonia borane (AB) dehydrogenation, which was not only enhanced from the pristine LT, but higher than conventional TiO2-based photocatalysts like Au-loaded P25.

Templated Synthesis of Exfoliated Porous Carbon with Dominant Graphitic Nitrogen.

We present here a new approach for the synthesis of nitrogen-doped porous graphitic carbon (g-NC) with a stoichiometry of C6.3H3.6N1.0O1.2, using layered silicate as a hard sacrificial template. Autogenous exfoliation is achieved due to the heterostacking of 2D silicate and nitrogen-doped carbon layers. Micro- and meso-porosity is induced by melamine and cetyltrimethylammonium (C16TMA). Our density functional calculations and X-ray photoelectron spectroscopy (XPS) observations confirm that the most dominant nitrogen configuration in g-CN is graphitic, while pyridinic and pyrrolic nitrogens are thermodynamically less favored. Our large-scale lattice dynamics calculations show that surface termination with H and OH groups at pores accounts for the observed H and O in the composition of the synthesized g-NC. We further evaluate the electrocatalytic and the supercapacitance activities of g-NC. Interestingly, this material exhibits a specific capacitance of ca. 202 F g-1 at 1 A g-1, retaining 90% of its initial capacitance after 10,000 cycles.

Tuning the metal-adsorbate chemical bond through the ligand effect on platinum subsurface alloys.

Scratching beneath the surface: Pt-M(3d)-Pt(111) (M(3d) = Co, Ni) bimetallic subsurface alloys have been designed to show the ligand effect tunes reactivity in oxygen and hydrogen adsorption systems. The platinum-oxygen bond order was investigated by oxygen atom projection in the occupied and unoccupied space using X-ray emission spectroscopy (XES) and X-ray absorption spectroscopy (XAS).

Modifying the Electron-Trapping Process at the BiVO4 Surface States via the TiO2 Overlayer for Enhanced Water Oxidation.

BiVO4 is one of the most promising photoanode candidates to achieve high-efficiency water splitting. However, overwhelming charge recombination at the interface limits its water oxidation activity. In this study, we show that the water oxidation activity of the BiVO4 photoanode is significantly boosted by the TiO2 overlayer prepared by atomic layer deposition. With a TiO2 overlayer of an optimized thickness, the photocurrent at 1.23 VRHE increased from 0.64 to 1.1 mA·cm-2 under front illumination corresponding to 72% enhancement. We attribute this substantial improvement to enhanced charge separation and suppression of surface recombination due to surface-state passivation. We provide direct evidence via transient photocurrent measurements that the TiO2 overlayer significantly decreases the photogenerated electron-trapping process at the BiVO4 surface. Electron-trapping passivation leads to enhanced electron photoconductivity, which results in higher photocurrent enhancement under front illumination rather than back illumination. This feature can be particularly useful for wireless tandem devices for water splitting as the higher band gap photoanodes are typically utilized with front illumination in such configurations. Even though the electron-trapping process is eliminated completely at higher TiO2 overlayer thicknesses, the charge-transfer resistance at the surface also increases significantly, resulting in a diminished photocurrent. We demonstrate that the ultrathin TiO2 overlayer can be used to fine tune the surface properties of BiVO4 and may be used for similar purposes for other photoelectrode systems and other photoelectrocatalytic reactions.

The Fast-Track Water Oxidation Channel on BiVO4 Opened by Nitrogen Treatment.

BiVO4 is one of the most promising photoanode materials for water-splitting systems. Nitrogen incorporation into a BiVO4 surface overcomes the known bottleneck in its charge-transfer kinetics into the electrolyte. We explored the role of nitrogen in the surface charge recombination and charge-transfer kinetics by employing transient photocurrent spectroscopy at the time scale of surface recombination and water oxidation kinetics, transient absorption spectroscopy, and X-ray photoelectron spectroscopy. We attributed the activity enhancement mechanism to the accelerated V5+/V4+ redox process, in which incorporated nitrogen suppresses a limiting surface recombination channel by increasing the oxygen vacancies.

Strong Light-Matter Interactions in Au Plasmonic Nanoantennas Coupled with Prussian Blue Catalyst on BiVO4 for Photoelectrochemical Water Splitting.

A facial and large-scale compatible fabrication route is established, affording a high-performance heterogeneous plasmonic-based photoelectrode for water oxidation that incorporates a CoFe-Prussian blue analog (PBA) structure as the water oxidation catalytic center. For this purpose, an angled deposition of gold (Au) was used to selectively coat the tips of the bismuth vanadate (BiVO4 ) nanostructures, yielding Au-capped BiVO4 (Au-BiVO4 ). The formation of multiple size/dimension Au capping islands provides strong light-matter interactions at nanoscale dimensions. These plasmonic particles not only enhance light absorption in the bulk BiVO4 (through the excitation of Fabry-Perot (FP) modes) but also contribute to photocurrent generation through the injection of sub-band-gap hot electrons. To substantiate the activity of the photoanodes, the interfacial electron dynamics are significantly improved by using a PBA water oxidation catalyst (WOC) resulting in an Au-BiVO4 /PBA assembly. At 1.23 V (vs. RHE), the photocurrent value for a bare BiVO4 photoanode was obtained as 190 µA cm-2 , whereas it was boosted to 295 µA cm-2 and 1800 µA cm-2 for Au-BiVO4 and Au-BiVO4 /PBA, respectively. Our results suggest that this simple and facial synthetic approach paves the way for plasmonic-based solar water splitting, in which a variety of common metals and semiconductors can be employed in conjunction with catalyst designs.

Strong Light-Matter Interactions in Au Plasmonic Nanoantennas Coupled with Prussian Blue Catalyst on BiVO4 for Photoelectrochemical Water Splitting.

Invited for this month's cover is the group of Ferdi Karadas and Ekmel Ozbay at Bilkent University. The image proposes a hybrid architecture, in which the semiconductor photoactive host is coupled to a plasmonic particle and a catalyst, to significantly substantiate the photoactivity of the cell. The Full Paper itself is available at 10.1002/cssc.202000294.