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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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.

High-Density Isolated Fe1O3 Sites on a Single-Crystal Cu2O(100) Surface.

Single-atom catalysts have recently been subject to considerable attention within applied catalysis. However, complications in the preparation of well-defined single-atom model systems have hampered efforts to determine the reaction mechanisms underpinning the reported activity. By means of an atomic layer deposition method utilizing the steric hindrance of the ligands, isolated Fe1O3 motifs were grown on a single-crystal Cu2O(100) surface at densities up to 0.21 sites per surface unit cell. Ambient pressure X-ray photoelectron spectroscopy shows a strong metal-support interaction with Fe in a chemical state close to 3+. Results from scanning tunneling microscopy and density functional calculations demonstrate that isolated Fe1O3 is exclusively formed and occupies a single site per surface unit cell, coordinating to two oxygen atoms from the Cu2O lattice and another through abstraction from O2. The isolated Fe1O3 motif is active for CO oxidation at 473 K. The growth method holds promise for extension to other catalytic systems.

Possibility of numt co-amplification from gigantic genome of Orthoptera: testing efficiency of standard PCR protocol in producing orthologous COI sequences.

Mitochondrial DNA has been the preferential genome biodiversity studies. However, several factors contribute to its inadequacy. Numts constitute one of the main complications that prevent obtaining orthologous mitochondrial sequences. Orthoptera have been a model group in numt studies because of their huge genome size. In this study we aimed to; (i) test efficiency of standard PCR protocol in producing orthologous sequences of cytochrome C oxidase, (ii) study presence/absence of numts in several unstudied Orthoptera species, (iii) test if there is a threshold between the length of mtDNA targeted for amplification and possibility of encountering numts, and (iv) estimate reliability of the sequences in databases in light of these findings. For these aims we studied 38 species of Orthoptera representing different sublineages and genome sizes. DNA extracted from each sample was used to amplify five different fragments of COI region by standard PCR protocol. Sequenced PCR amplicons were checked for numt possibility by several different numt criteria. No sequences without numt signs were obtained for the first fragment. The number of samples with numt signs for the other four fragments differed between the suborders Ensifera and Caelifera. The percentage of samples with numt signs was higher in Caelifera than Ensifera for all fragments. The numt percentage considerably decreased for the longest two fragments. Numts are more prevalent in families with larger genome size. We arrived at the following conclusions: (i) numts are common in all members of Orthoptera, but, their prevalence differs among intra-lineages, especially more prevalent in Caelifera, (ii) there seems a correlation between numt rate and genome size, (iii) there is no threshold to avoid numt co-amplification, but, a 1,000 bp length may be a threshold for Ensifera, (iv) Folmer region of COI doesn't seem an appropriate marker for animal barcoding. Additionally, a phylogenetic tree produced from the numt sequences of fragment four detected in genus Anterastes suggested a paleonumt gained in generic ancestor a 3.5-4 times slower divergence rate for numt sequences.

Review of Poecilimon species with inflated pronotum: description of four new taxa within an acoustically diverse group.

Poecilimon Fischer (Orthoptera, Tettigoniidae) consists of about 130 species and a functional taxonomy of the genus requires arranging species into phylogenetic groups. However, this is a task that requires detailed empirical testing. This paper documents data on Poecilimon species with an inflated pronotum. The Poecilimon (Poecilimon) inflatus group is a lineage ranging along a narrow zone in the south-west corner of Anatolia and in Crete plus some other Aegean islands. By producing data of morphology and calling songs of males and responding songs of females the composition and intra-group diversity of P. inflatus group are studied. Both morphology and male calling and female responding songs, exhibited a considerable intra-group diversity. In the light of data obtained the following nomenclatural changes were made. The genus Parapoecilimon Karabag, 1975 syn. n. is synonymised with Poecilimon Fischer and Parapoecilimon antalyaensis Karabag, 1975 is given a new combination, Poecilimon antalyaensis (Karabag, 1975) comb. n. Four new taxa are described in the group: (i) Poecilimon isopterus sp.n.; (ii) Poecilimon inflatus lyciae subsp. n.; (iii) Poecilimon antalyaensis myrae subsp. n., and (iv) Poecilimon antalyaensis anemurium subsp. n. The Poecilimon (P.) inflatus species group consists of the following species: (i) Poecilimon inflatus Brunner von Wattenwyl, 1891; (ii) Poecilimon martinae Heller, 2004; (iii) Poecilimon cretensis Werner, 1903; (iv) Poecilimon antalyaensis (Karabag, 1975) comb. n.; (v) Poecilimon bilgeri Karabag, 1953 and (vi) Poecilimon isopterus sp.n. The species group is defined by a combination of characters including the pronotum inflated in metazona and a male cerci mostly black in their apical 1/2-1/3. The male calling song has typically two types of short syllables and the females respond acoustically with very short latency times. By using combination of morphology and song data we suggest three main lineages in the group: (i) P. bilgeri, (ii) P. antalyaensis and (iii) the other four species.

Synergistic cooperation and crosstalk between MYD88L265P and mutations that dysregulate CD79B and surface IgM.

CD79B and MYD88 mutations are frequently and simultaneously detected in B cell malignancies. It is not known if these mutations cooperate or how crosstalk occurs. Here we analyze the consequences of CD79B and MYD88L265P mutations individually and combined in normal activated mouse B lymphocytes. CD79B mutations alone increased surface IgM but did not enhance B cell survival, proliferation, or altered NF-κB responsive markers. Conversely, B cells expressing MYD88L265P decreased surface IgM coupled with accumulation of endoglycosidase H-sensitive IgM intracellularly, resembling the trafficking block in anergic B cells repeatedly stimulated by self-antigen. Mutation or overexpression of CD79B counteracted the effect of MYD88L265P In B cells chronically stimulated by self-antigen, CD79B and MYD88L265P mutations in combination, but not individually, blocked peripheral deletion and triggered differentiation into autoantibody secreting plasmablasts. These results reveal that CD79B and surface IgM constitute a rate-limiting checkpoint against B cell dysregulation by MYD88L265P and provide an explanation for the co-occurrence of MYD88 and CD79B mutations in lymphomas.

Chemical Bond Activation Observed with an X-ray Laser.

The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free-electron laser to directly observe the decreased bonding-antibonding splitting following bond-activation using an ultrashort optical laser pulse.

Contribution to the taxonomy of Poecilimon bosphoricus species group (Orthoptera: Phaneropteridae): two new species from its core range.

The Poecilimon bosphoricus species group, representing the most diverse lineage of the bushcricket genus Poecilimon, has been studied in the Basin of Marmara Sea. Two new species, P. warchalowskae sp. n. and P. canakkale sp. n., are described morphologically and acoustically in comparison to their related taxa of the P. bosphoricus species group. Song type and morphology of the new species suggests that they are related to P. turcicus, P. turciae and P. athos and each of these five species can be distinguished by their specific male cerci. The diagnoses are supplemented with comparative figures of morphology and song. Additionally, a short account is given on the synonymy of P. anatolicus with P. sureyanus.

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.