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1.
EMBO J ; 43(18): 4020-4048, 2024 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-39134659

RESUMO

Sex determination in animals is not only determined by karyotype but can also be modulated by environmental cues like temperature via unclear transduction mechanisms. Moreover, in contrast to earlier views that sex may exclusively be determined by either karyotype or temperature, recent observations suggest that these factors rather co-regulate sex, posing another mechanistic mystery. Here, we discovered that certain wild-isolated and mutant C. elegans strains displayed genotypic germline sex determination (GGSD), but with a temperature-override mechanism. Further, we found that BiP, an ER chaperone, transduces temperature information into a germline sex-governing signal, thereby enabling the coexistence of GGSD and temperature-dependent germline sex determination (TGSD). At the molecular level, increased ER protein-folding requirements upon increased temperatures lead to BiP sequestration, resulting in ERAD-dependent degradation of the oocyte fate-driving factor, TRA-2, thus promoting male germline fate. Remarkably, experimentally manipulating BiP or TRA-2 expression allows to switch between GGSD and TGSD. Physiologically, TGSD allows C. elegans hermaphrodites to maintain brood size at warmer temperatures. Moreover, BiP can also influence germline sex determination in a different, non-hermaphroditic nematode species. Collectively, our findings identify thermosensitive BiP as a conserved temperature sensor in TGSD, and provide mechanistic insights into the transition between GGSD and TGSD.


Assuntos
Proteínas de Caenorhabditis elegans , Caenorhabditis elegans , Células Germinativas , Processos de Determinação Sexual , Temperatura , Animais , Caenorhabditis elegans/genética , Caenorhabditis elegans/metabolismo , Proteínas de Caenorhabditis elegans/metabolismo , Proteínas de Caenorhabditis elegans/genética , Masculino , Células Germinativas/metabolismo , Feminino , Proteínas de Choque Térmico/metabolismo , Proteínas de Choque Térmico/genética
2.
Mol Cell ; 73(3): 601-610.e5, 2019 02 07.
Artigo em Inglês | MEDLINE | ID: mdl-30595438

RESUMO

CRISPR-Cas immune systems utilize RNA-guided nucleases to protect bacteria from bacteriophage infection. Bacteriophages have in turn evolved inhibitory "anti-CRISPR" (Acr) proteins, including six inhibitors (AcrIIA1-AcrIIA6) that can block DNA cutting and genome editing by type II-A CRISPR-Cas9 enzymes. We show here that AcrIIA2 and its more potent homolog, AcrIIA2b, prevent Cas9 binding to DNA by occluding protein residues required for DNA binding. Cryo-EM-determined structures of AcrIIA2 or AcrIIA2b bound to S. pyogenes Cas9 reveal a mode of competitive inhibition of DNA binding that is distinct from other known Acrs. Differences in the temperature dependence of Cas9 inhibition by AcrIIA2 and AcrIIA2b arise from differences in both inhibitor structure and the local inhibitor-binding environment on Cas9. These findings expand the natural toolbox for regulating CRISPR-Cas9 genome editing temporally, spatially, and conditionally.


Assuntos
Proteína 9 Associada à CRISPR/metabolismo , Sistemas CRISPR-Cas , DNA/metabolismo , Edição de Genes/métodos , Fagos de Pseudomonas/metabolismo , Pseudomonas aeruginosa/enzimologia , RNA Guia de Cinetoplastídeos/metabolismo , Temperatura , Proteínas Virais/metabolismo , Ligação Competitiva , Proteína 9 Associada à CRISPR/antagonistas & inibidores , Proteína 9 Associada à CRISPR/genética , Proteína 9 Associada à CRISPR/ultraestrutura , Microscopia Crioeletrônica , DNA/genética , DNA/ultraestrutura , Escherichia coli/enzimologia , Escherichia coli/genética , Regulação Bacteriana da Expressão Gênica , Modelos Moleculares , Conformação de Ácido Nucleico , Ligação Proteica , Conformação Proteica , Fagos de Pseudomonas/genética , Pseudomonas aeruginosa/genética , Pseudomonas aeruginosa/virologia , RNA Guia de Cinetoplastídeos/genética , RNA Guia de Cinetoplastídeos/ultraestrutura , Relação Estrutura-Atividade , Proteínas Virais/genética , Proteínas Virais/ultraestrutura
3.
Proc Natl Acad Sci U S A ; 121(37): e2401752121, 2024 Sep 10.
Artigo em Inglês | MEDLINE | ID: mdl-39226347

RESUMO

Ovarian development was traditionally recognized as a "default" sexual outcome and therefore received much less scientific attention than testis development. In turtles with temperature-dependent sex determination (TSD), how the female pathway is initiated to induce ovary development remains unknown. In this study, we have found that phosphorylation of the signal transducer and activator of transcription 3 (pSTAT3) and Foxl2 exhibit temperature-dependent sexually dimorphic patterns and tempo-spatial coexpression in early embryos of the red-eared slider turtle (Trachemys scripta elegans). Inhibition of pSTAT3 at a female-producing temperature of 31 °C induces 64.7% female-to-male sex reversal, whereas activation of pSTAT3 at a male-producing temperature of 26 °C triggers 75.6% male-to-female sex reversal. In addition, pSTAT3 directly binds to the locus of the female sex-determining gene Foxl2 and promotes Foxl2 transcription. Overexpression or knockdown of Foxl2 can rescue the sex reversal induced by inhibition or activation of pSTAT3. This study has established a direct genetic link between warm temperature-induced STAT3 phosphorylation and female pathway initiation in a TSD system, highlighting the critical role of pSTAT3 in the cross talk between female and male pathways.


Assuntos
Fator de Transcrição STAT3 , Processos de Determinação Sexual , Temperatura , Tartarugas , Animais , Feminino , Fator de Transcrição STAT3/metabolismo , Fator de Transcrição STAT3/genética , Masculino , Fosforilação , Tartarugas/metabolismo , Tartarugas/genética , Tartarugas/embriologia , Ovário/metabolismo , Fatores de Transcrição Forkhead/metabolismo , Fatores de Transcrição Forkhead/genética , Proteína Forkhead Box L2/metabolismo , Proteína Forkhead Box L2/genética , Regulação da Expressão Gênica no Desenvolvimento
4.
Trends Genet ; 39(4): 242-250, 2023 04.
Artigo em Inglês | MEDLINE | ID: mdl-36669949

RESUMO

Genetic sex determination (SD) in most vertebrates is controlled by a single master sex gene, which ensures a 1:1 sex ratio. However, more complex systems abound, and several have been ascribed to polygenic SD (PSD), in which many genes at different loci interact to produce the sexual phenotype. Here we examine claims for PSD in vertebrates, finding that most constitute transient states during sex chromosome turnover, or aberrant systems in species hybrids. To avoid confusion about terminology, we propose a consistent nomenclature for genetic SD systems.


Assuntos
Processos de Determinação Sexual , Vertebrados , Animais , Processos de Determinação Sexual/genética , Vertebrados/genética , Cromossomos Sexuais/genética , Herança Multifatorial/genética , Fenótipo
5.
Dev Biol ; 514: 99-108, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-38914191

RESUMO

Fifty years ago, researchers discovered a link between ambient temperature and the sex of turtle embryos. More recently, significant progress has been made in understanding the influence of temperature on freshwater turtles. However, our understanding of the key genetic factors in other turtle groups, such as sea turtles, remains limited. To address this gap, we conducted RNA-seq analyses on embryonic tissues from the sea olive ridley turtle during the thermosensitive period (stages 21-26) at temperatures known to produce males (26 °C) and females (33 °C). Our findings revealed that incubation temperatures primarily influence genes with broad expression across tissues due to differential cell division rates and later have an effect regulating gonad-specific transcripts. This effect is mostly related to gene activation rather than transcription repression. We performed transcriptome analyses following shifts in incubation temperatures of bi-potential gonads. This approach allowed us to identify genes that respond rapidly and may be closer to the beginning of the temperature-sensing pathway. Notably, we observed swift adaptations in the expression levels of chromatin modifiers JARID2 and KDM6B, as well as the splicing factor SRSF5, and transcription regulators THOC2, DDX3X and CBX3, but little impact in the overall gonad-specific pathways, indicating that temperature-sensing genes may change rapidly but the rewiring of the gonad's developmental fate is complex and resilient. AUTHOR SUMMARY: Sea turtles, one of the most iconic creatures of our oceans, confront a troubling reality of endangerment, a peril magnified by the looming specter of climate change. This climatic shift is gradually increasing the temperature of the nesting beaches thus causing dramatic male/female population biases. Conservation efforts will need genetic and molecular information to reverse the negative effects of climate change on the populations. In this study, we conducted the first transcriptomic analysis of embryonic tissues, including gonads, brain, liver, and mesonephros, in the olive ridley sea turtle during the critical thermosensitive period spanning stages 21-26. We examined both male-producing (26 °C) and female-producing (33 °C) temperatures and found that incubation temperatures influence temperature-sensitive genes that are either expressed globally or specifically associated with the gonads. These findings indicate that incubation temperatures predominantly sway genes with broad expression patterns due to differential cell division rates. This natural process was opted in the gonads to drive sex determination. We also identified genes that are rapidly capable of sensing temperature changes and that could play a role in the activation of the sex determination pathway. Overall, our study sheds light on the intricate interplay between temperature and gene expression during sea turtle development, revealing dynamic changes in the transcriptome and highlighting the involvement of key genetic players in sex determination.


Assuntos
Regulação da Expressão Gênica no Desenvolvimento , Gônadas , Processos de Determinação Sexual , Temperatura , Tartarugas , Animais , Tartarugas/embriologia , Tartarugas/genética , Processos de Determinação Sexual/genética , Masculino , Feminino , Gônadas/metabolismo , Gônadas/embriologia , Transcriptoma/genética , Perfilação da Expressão Gênica , Embrião não Mamífero/metabolismo
6.
Development ; 149(13)2022 07 01.
Artigo em Inglês | MEDLINE | ID: mdl-35819065

RESUMO

KDM6B-mediated epigenetic modification of the testicular regulator Dmrt1 has previously been identified as the primary switch of the male pathway in a temperature-dependent sex-determination (TSD) system; however, the molecular network of the female pathway has not yet been established. Here, we have functionally characterized for the first time an upstream regulator of the female pathway, the forkhead transcription factor FOXL2, in Trachemys scripta, a turtle species with a TSD system. FOXL2 exhibited temperature-dependent female-specific expression patterns before the onset of gonadal differentiation and was preferentially localized in ovarian somatic cells. Foxl2 responded rapidly to temperature shifts and estrogen. Importantly, forced expression of Foxl2 at the male-producing temperature led to male-to-female sex reversal, as evidenced by the formation of an ovary-like structure, and upregulation of the ovarian regulators Cyp19a1 and R-spondin1. Additionally, knockdown of Foxl2 caused masculinization at the female-producing temperature, which was confirmed by loss of the female phenotype, development of seminiferous tubules, and elevated expression of Dmrt1 and Sox9. Collectively, we demonstrate that Foxl2 expression is necessary and sufficient to drive ovarian determination in T. scripta, suggesting a crucial role of Foxl2 in female sex determination in the TSD system.


Assuntos
Tartarugas , Animais , Feminino , Regulação da Expressão Gênica no Desenvolvimento , Gônadas/metabolismo , Masculino , Processos de Determinação Sexual/genética , Diferenciação Sexual/genética , Temperatura , Tartarugas/genética
7.
Nano Lett ; 24(20): 6061-6068, 2024 May 22.
Artigo em Inglês | MEDLINE | ID: mdl-38728017

RESUMO

van der Waals (vdW) superlattices, comprising different 2D materials aligned alternately by weak interlayer interactions, offer versatile structures for the fabrication of novel semiconductor devices. Despite their potential, the precise control of optoelectronic properties with interlayer interactions remains challenging. Here, we investigate the discrepancies between the SnS/TiS2 superlattice (SnTiS3) and its subsystems by comprehensive characterization and DFT calculations. The disappearance of certain Raman modes suggests that the interactions alter the SnS subsystem structure. Specifically, such structural changes transform the band structure from indirect to direct band gap, causing a strong PL emission (∼2.18 eV) in SnTiS3. In addition, the modulation of the optoelectronic properties ultimately leads to the unique phenomenon of thermally activated photoluminescence. This phenomenon is attributed to the inhibition of charge transfer induced by tunable intralayer strains. Our findings extend the understanding of the mechanism of interlayer interactions in van der Waals superlattices and provide insights into the design of high-temperature optoelectronic devices.

8.
Nano Lett ; 24(11): 3347-3354, 2024 Mar 20.
Artigo em Inglês | MEDLINE | ID: mdl-38451030

RESUMO

Understanding the photosensitization mechanisms in Yb3+-doped perovskite nanocrystals is crucial for developing their anticipated photonic applications. Here, we address this question by investigating near-infrared photoluminescence of Yb3+-doped mixed-halide CsPbClxBr3-x nanocrystals as a function of temperature and revealing its strong dependence on the stoichiometry of the host perovskite matrix. To explain the observed experimental trends, we developed a theoretical model in which energy transfer from the perovskite matrix to Yb3+ ions occurs through intermediate trap states situated beneath the conduction band of the host. The developed model provides an excellent agreement with experimental results and is further validated through the measurements of emission saturation at high excitation powers and near-infrared photoluminescence quantum yield as a function of the anion composition. Our findings establish trap-mediated energy transfer as a dominant photosensitization mechanism in Yb3+-doped CsPbClxBr3-x nanocrystals and open up new ways of engineering their optical properties for light-emitting and light-harvesting applications.

9.
J Biol Chem ; 299(12): 105433, 2023 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-37926286

RESUMO

DNA methylation provides an important epigenetic mechanism that critically regulates gene expression, genome imprinting, and retrotransposon silencing. In plants, DNA methylation is prevalent not only in a CG dinucleotide context but also in non-CG contexts, namely CHG and CHH (H = C, T, or A) methylation. It has been established that plant non-CG DNA methylation is highly context dependent, with the +1- and +2-flanking sequences enriched with A/T nucleotides. How DNA sequence, conformation, and dynamics influence non-CG methylation remains elusive. Here, we report structural and biochemical characterizations of the intrinsic substrate preference of DOMAINS REARRANGED METHYLTRANSFERASE 2 (DRM2), a plant DNA methyltransferase responsible for establishing all cytosine methylation and maintaining CHH methylation. Among nine CHH motifs, the DRM2 methyltransferase (MTase) domain shows marked substrate preference toward CWW (W = A or T) motifs, correlating well with their relative abundance in planta. Furthermore, we report the crystal structure of DRM2 MTase in complex with a DNA duplex containing a flexible TpA base step at the +1/+2-flanking sites of the target nucleotide. Comparative structural analysis of the DRM2-DNA complexes provides a mechanism by which flanking nucleotide composition impacts DRM2-mediated DNA methylation. Furthermore, the flexibility of the TpA step gives rise to two alternative DNA conformations, resulting in different interactions with DRM2 and consequently temperature-dependent shift of the substrate preference of DRM2. Together, this study provides insights into how the interplay between the conformational dynamics of DNA and temperature as an environmental factor contributes to the context-dependent CHH methylation by DRM2.


Assuntos
Arabidopsis , Arabidopsis/metabolismo , DNA/metabolismo , Metilação de DNA , DNA de Plantas/metabolismo , Regulação da Expressão Gênica de Plantas , Metiltransferases/genética , Metiltransferases/metabolismo , Conformação de Ácido Nucleico , Nucleotídeos/metabolismo
10.
Plant J ; 114(3): 613-635, 2023 05.
Artigo em Inglês | MEDLINE | ID: mdl-36799458

RESUMO

As an essential enzyme in the uridine diphosphate (UDP)-GlcNAc biosynthesis pathway, the significant role of N-acetylglucosamine phosphate mutase (AGM) remains unknown in plants. In the present study, a functional plant AGM (AtAGM) was identified from Arabidopsis thaliana. AtAGM catalyzes the isomerization of GlcNAc-1-P and GlcNAc-6-P, and has broad catalytic activity on different phosphohexoses. UDP-GlcNAc contents were significantly decreased in AtAGM T-DNA insertional mutants, which caused temperature-dependent growth defects in seedlings and vigorous growth in adult plants. Further analysis revealed that protein O-GlcNAcylation but not N-glycosylation was dramatically impaired in Atagm mutants due to UDP-GlcNAc shortage. Combined with the results from O-GlcNAcylation or N-glycosylation deficient mutants, and O-GlcNAcase inhibitor all suggested that protein O-GlcNAcylation impairment mainly leads to the phenotypic variations of Atagm plants. In conclusion, based on the essential role in UDP-GlcNAc biosynthesis, AtAGM is important for plant growth mainly via protein O-GlcNAcylation-level regulation.


Assuntos
Arabidopsis , Arabidopsis/metabolismo , Acetilglucosamina/metabolismo , Proteínas/metabolismo , Glicosilação , Fosfatos/metabolismo , Processamento de Proteína Pós-Traducional
11.
BMC Genomics ; 25(1): 383, 2024 Apr 18.
Artigo em Inglês | MEDLINE | ID: mdl-38637759

RESUMO

BACKGROUND: The Asian yellow pond turtle (Mauremys mutica) is an important commercial freshwater aquaculture species in China. This species is a highly sexually dimorphic species, with males growing at a faster rate than females and exhibits temperature-dependent sex determination (TSD), in which the incubation temperature during embryonic development determines the sexual fate. However, the mechanisms of the sex determination or sex differentiation in the Asian yellow pond turtle are remain a mystery. RESULTS: Temperature-specific gonadal transcriptomics of the Asian yellow pond turtle were performed during the thermosensitive period (stage 15) using RNA-seq technology to identify candidate genes that initiate gonadal differentiation. We uncovered candidates that were the first to respond to temperature. These candidates were sexually dimorphic in expression, reflecting differences in gonadal (Cirbp, Runx1) and germline differentiation (Vasa, Nanos1, Piwil2), gametogenesis (Hmgb3, Zar1, Ovoinhibitor-like, Kif4), steroid hormone biosynthesis (Hsd17b5, Hsd17b6), heat shock (Dnajb6, Hsp90b1, Hsp90aa1) and transient receptor potential channel genes (Trpm1, Trpm4, Trpm6, Trpv1). CONCLUSIONS: Our work will provide important genetic information to elucidate the mechanisms of sex control in the Asian yellow pond turtles, and will contribute important genetic resources for further studies of temperature-dependent sex determination in turtles.


Assuntos
Diferenciação Sexual , Tartarugas , Masculino , Animais , Feminino , Diferenciação Sexual/genética , Tartarugas/genética , Temperatura , Perfilação da Expressão Gênica , Desenvolvimento Embrionário
12.
BMC Genomics ; 25(1): 221, 2024 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-38418960

RESUMO

BACKGROUND: Wheat streak mosaic virus (WSMV) and Triticum mosaic virus (TriMV) are components of the wheat streak mosaic virus disease complex in the Great Plains region of the U.S.A. and elsewhere. Co-infection of wheat with WSMV and TriMV causes synergistic interaction with more severe disease symptoms compared to single infections. Plants are equipped with multiple antiviral mechanisms, of which regulation of microRNAs (miRNAs) is a potentially effective constituent. In this investigation, we have analyzed the total and relative expression of miRNA transcriptome in two wheat cultivars, Arapahoe (susceptible) and Mace (temperature-sensitive-resistant), that were mock-inoculated or inoculated with WSMV, TriMV, or both at 18 °C and 27 °C. RESULTS: Our results showed that the most abundant miRNA family among all the treatments was miRNA166, followed by 159a and 168a, although the order of the latter two changed depending on the infections. When comparing infected and control groups, twenty miRNAs showed significant upregulation, while eight miRNAs were significantly downregulated. Among them, miRNAs 9670-3p, 397-5p, and 5384-3p exhibited the most significant upregulation, whereas miRNAs 319, 9773, and 9774 were the most downregulated. The comparison of infection versus the control group for the cultivar Mace showed temperature-dependent regulation of these miRNAs. The principal component analysis confirmed that less abundant miRNAs among differentially expressed miRNAs were strongly correlated with the inoculated symptomatic wheat cultivars. Notably, miRNAs 397-5p, 398, and 9670-3p were upregulated in response to WSMV and TriMV infections, an observation not yet reported in this context. The significant upregulation of these three miRNAs was further confirmed with RT-qPCR analysis; in general, the RT-qPCR results were in agreement with our computational analysis. Target prediction analysis showed that the miRNAs standing out in our analysis targeted genes involved in defense response and regulation of transcription. CONCLUSION: Investigation into the roles of these miRNAs and their corresponding targets holds promise for advancing our understanding of the mechanisms of virus infection and possible manipulation of these factors for developing durable virus resistance in crop plants.


Assuntos
MicroRNAs , Potyviridae , MicroRNAs/genética , Doenças das Plantas/genética , Potyviridae/genética
13.
New Phytol ; 241(2): 845-860, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37920100

RESUMO

Specificity in plant-pathogen gene-for-gene (GFG) interactions is determined by the recognition of pathogen proteins by the products of plant resistance (R) genes. The evolutionary dynamics of R genes in plant-virus systems is poorly understood. We analyse the evolution of the L resistance locus to tobamoviruses in the wild pepper Capsicum annuum var. glabriusculum (chiltepin), a crop relative undergoing incipient domestication. The frequency, and the genetic and phenotypic diversity, of the L locus was analysed in 41 chiltepin populations under different levels of human management over its distribution range in Mexico. The frequency of resistance was lower in Cultivated than in Wild populations. L-locus genetic diversity showed a strong spatial structure with no isolation-by-distance pattern, suggesting environment-specific selection, possibly associated with infection by the highly virulent tobamoviruses found in the surveyed regions. L alleles differed in recognition specificity and in the expression of resistance at different temperatures, broad-spectrum recognition of P0 + P1 pathotypes and expression above 32°C being ancestral traits that were repeatedly lost along L-locus evolution. Overall, loss of resistance co-occurs with incipient domestication and broad-spectrum resistance expressed at high temperatures has apparent fitness costs. These findings contribute to understand the role of fitness trade-offs in plant-virus coevolution.


Assuntos
Capsicum , Resistência à Doença , Humanos , Resistência à Doença/genética , Temperatura , Alelos , México , Capsicum/genética , Doenças das Plantas/genética
14.
Chemistry ; 30(14): e202303267, 2024 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-38168472

RESUMO

Developing new electrode materials with good temperature-dependent electrochemical performance has become a great issue for the deployment of hybrid supercapacitors with wide temperature tolerance. In this work, a series of Ta-substituted SrCo1-x Tax O3-δ (x=0.05, 0.10, 0.15, 0.20) perovskites have been studied as positive electrodes for hybrid supercapacitors in terms of their structures, elemental valence states and electrochemical performances. Incorporating Ta into SrCoO3-δ perovskite not only stabilizes the crystallite structure but also notably improves electrochemical activities. The SrCo0.95 Ta0.05 O3-δ @CC delivers the highest specific capacity (Qsp ) of 227.91 C g-1 at 1 A g-1 , which is attributed to the highest oxygen vacancy content and the fastest oxygen diffusion kinetics. The hybrid supercapacitor SrCo0.95 Ta0.05 O3-δ @CC//AC@CC exhibits a high energy density of 22.82 Wh kg-1 @775.09 W kg-1 and a stable long-term cycle life (5000 cycles) with 90.7 % capacity retention. As temperature increases from 25 to 85 °C, the capacitance properties are improved at elevated temperatures for both electrode and device due to the increased electrolyte conductivity. The outstanding electrochemical results present that SrCo1-x Tax O3-δ perovskite holds good prospects for hybrid supercapacitors with wide temperature tolerance.

15.
Chemistry ; : e202403060, 2024 Oct 10.
Artigo em Inglês | MEDLINE | ID: mdl-39390662

RESUMO

Two Co-based supramolecular isomers were synthesized from a fluorinated carboxylic acid ligand under hydrothermal conditions at varying temperatures. Both exhibited similar one-dimensional chain structures while different bending connections of the aromatic rings led to different supramolecular structures, namely CoCP-1 and CoCP-2, respectively. The structural differences of two isomers resulted in discrepant performance with regards to luminescence sensing and catalysis. CoCP-1 demonstrated more significant luminescence quenching activity toward biomarkers 2,6-dipyridinoic acid (DPA) and high vanilloid acid (HVA), which could be distinguished in the presence of Eu3+. The limit of detection (LOD) was found to be as low as 3.4 and 1.3 µM, respectively. The recovery rate of for HVA and DPA was within the range of 89.6-101.2% and 99.7-117.9% in simulated urine and serum, respectively, indicating potential reliability in monitoring these two analytes in real samples. Notably, CoCP-2 exhibited catalytic activity for the oxidation of thioethers to sulfoxides. Our finding here suggests that the coordination conformation of the ligands within supramolecular isomers plays a pivotal role in determining the structure and luminescence sensing/catalysis performance.

16.
Chemphyschem ; 25(1): e202300467, 2024 Jan 02.
Artigo em Inglês | MEDLINE | ID: mdl-37916391

RESUMO

This computational study of line-broadening effects is based on an accurate, analytical representation of the intermonomer potential energy surface (PES) of the CO2 ⋅ Ar van der Waals (vdW) complex. The PES is employed to compute collisional broadening coefficients for rovibrational lines of CO2 perturbed by Ar. The semiclassical computations are performed using the modified Robert-Bonamy approach, including real and imaginary terms, and the exact trajectory model. The lines investigated are in the 10001←00011, 01101←00001, 00011←00001, and 00031←00001 vibrational bands and the computations are repeated at multiple temperatures. The computed results are in good agreement with the available experimental values, validating both the intermonomer PES developed and the methodology used. For lines in the 01101←00001 band of CO2 , temperature-dependent Ar-broadening coefficients are reported for the first time. The parameters presented should prove useful, among other applications, for the accurate experimental determination of CO2 and Ar abundances in planetary atmospheres.

17.
Chemphyschem ; 25(20): e202400286, 2024 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-38895746

RESUMO

We present structural properties at different temperatures and high-pressure (HP) of La3Rh4Sn13 which is one of the interesting systems in the Remika phase RE3Rh4Sn13 (RE=Sr, Ca, La, Pr, Ce) quasi-skutterudite series using synchrotron diffraction. Data at ambient conditions revealed the presence of several weak reflections, which could be accounted only with a superlattice I* structure (I4132) with lattice parameter a~19.457 Å. However, above 350 K, a complete suppression of the weak superlattice reflections of the I* structure is observed. Data at higher temperatures is found to be well described by the I structure (Pm-3n) having half the lattice parameter compared to the I* structure. HP-XRPD at ambient temperature showed that pressures greater than 7.5 GPa result in similar suppression of the weak I* superlattice reflections. Data at higher pressures is found to be well described by the I structure (Pm-3n), similar to the high-temperature phase. HP Raman measurements demonstrated changes that seem to be consistent with a locally more ordered structure as in the case of the I*→I transition. Our findings on La3Rh4Sn13 open up new avenues to study unexplored HP phenomena, especially the superconductivity in these Remika phase quasi-skutterudites.

18.
Bull Entomol Res ; 114(1): 8-21, 2024 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-38235528

RESUMO

Mosquito-borne disease is a significant public health issue and within Australia Ross River virus (RRV) is the most reported. This study combines a mechanistic model of mosquito development for two mosquito vectors; Aedes vigilax and Aedes camptorhynchus, with climate projections from three climate models for two Representative Concentration Pathways (RCPs), to examine the possible effects of climate change and sea-level rise on a temperate tidal saltmarsh habitat in Perth, Western Australia. The projections were run under no accretion and accretion scenarios using a known mosquito habitat as a case study. This improves our understanding of the possible implications of sea-level rise, accretion and climate change for mosquito control programmes for similar habitats across temperate tidal areas found in Southwest Western Australia. The output of the model indicate that the proportion of the year mosquitoes are active increases. Population abundances of the two Aedes species increase markedly. The main drivers of changes in mosquito population abundances are increases in the frequency of inundation of the tidal wetland and size of the area inundated, increased minimum water temperature, and decreased daily temperature fluctuations as water depth increases due to sea level changes, particularly under the model with no accretion. The effects on mosquito populations are more marked for RCP 8.5 when compared to RCP 4.5 but were consistent among the three climate change models. The results indicate that Ae. vigilax is likely to be the most abundant species in 2030 and 2050, but that by 2070 Aedes camptorhynchus may become the more abundant species. This increase would put considerable pressure on existing mosquito control programmes and increase the risk of mosquito-borne disease and nuisance biting to the local community, and planning to mitigate these potential impacts should commence now.


Assuntos
Aedes , Culicidae , Animais , Austrália Ocidental , Modelos Climáticos , Mudança Climática , Água
19.
Adv Exp Med Biol ; 1461: 109-125, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-39289277

RESUMO

Voltage-gated proton channel (Hv) has activity of proton transport following electrochemical gradient of proton. Hv is expressed in neutrophils and macrophages of which functions are physiologically temperature-sensitive. Hv is also expressed in human sperm cells and regulates their locomotion. H+ transport through Hv is both regulated by membrane potential and pH difference across biological membrane. It is also reported that properties of Hv such as proton conductance and gating are highly temperature-dependent. Hv consists of the N-terminal cytoplasmic domain, the voltage sensor domain (VSD), and the C-terminal coiled-coil domain, and H+ permeates through VSD voltage-dependently. The functional unit of Hv is a dimer via the interaction between C-terminal coiled-coils assembly domain. We have reported that the coiled-coil domain of Hv has the nature of dissociation around our bodily temperature and mutational change of the coiled-coil affected temperature-sensitive gating, especially its temperature threshold. The temperature-sensitive gating is assessed from two separate points: temperature threshold and temperature dependence. In this chapter, I describe physiological roles and molecular structure mechanisms of Hv by mainly focusing on thermosensitive properties.


Assuntos
Ativação do Canal Iônico , Canais Iônicos , Prótons , Temperatura , Humanos , Canais Iônicos/metabolismo , Canais Iônicos/química , Canais Iônicos/genética , Animais , Potenciais da Membrana/fisiologia , Concentração de Íons de Hidrogênio , Domínios Proteicos
20.
Proc Natl Acad Sci U S A ; 118(41)2021 10 12.
Artigo em Inglês | MEDLINE | ID: mdl-34607946

RESUMO

The decline in background extinction rates of marine animals through geologic time is an established but unexplained feature of the Phanerozoic fossil record. There is also growing consensus that the ocean and atmosphere did not become oxygenated to near-modern levels until the mid-Paleozoic, coinciding with the onset of generally lower extinction rates. Physiological theory provides us with a possible causal link between these two observations-predicting that the synergistic impacts of oxygen and temperature on aerobic respiration would have made marine animals more vulnerable to ocean warming events during periods of limited surface oxygenation. Here, we evaluate the hypothesis that changes in surface oxygenation exerted a first-order control on extinction rates through the Phanerozoic using a combined Earth system and ecophysiological modeling approach. We find that although continental configuration, the efficiency of the biological carbon pump in the ocean, and initial climate state all impact the magnitude of modeled biodiversity loss across simulated warming events, atmospheric oxygen is the dominant predictor of extinction vulnerability, with metabolic habitat viability and global ecophysiotype extinction exhibiting inflection points around 40% of present atmospheric oxygen. Given this is the broad upper limit for estimates of early Paleozoic oxygen levels, our results are consistent with the relative frequency of high-magnitude extinction events (particularly those not included in the canonical big five mass extinctions) early in the Phanerozoic being a direct consequence of limited early Paleozoic oxygenation and temperature-dependent hypoxia responses.


Assuntos
Organismos Aquáticos/crescimento & desenvolvimento , Atmosfera/química , Extinção Biológica , Temperatura Alta , Oxigênio/análise , Animais , Biodiversidade , Evolução Biológica , Ciclo do Carbono/fisiologia , Clima , Planeta Terra , Ecossistema , Fósseis , Oceanos e Mares , Água do Mar/química
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