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1.
Dalton Trans ; 53(25): 10511-10520, 2024 Jun 25.
Artigo em Inglês | MEDLINE | ID: mdl-38841884

RESUMO

Homoleptic complexes [Fe(4bt)3](ClO4)2 (1), [Fe(2bt)3](ClO4)2 (2), and [Fe(3tpH)3](ClO4)2 (3) were obtained by a reaction between the Fe(II) precursor salt and the corresponding thiazole-based bidentate ligand (L = 4bt = 4,4'-bithiazole, 2bt = 2,2'-bithiazole, 3tpH = 3-(thiazol-2-yl)pyrazole). X-ray crystal structure determination revealed crystallization of solvent-free complex 1, a solvate 2·MeOH, and a co-crystal 3·2(3tpH). The crystal packing of all these complexes is dominated by one-dimensional interactions between the [Fe(L)3]2+ cations. These interactions are stronger in 2·MeOH and 3·2(3tpH), leading to cooperative and slightly hysteretic transitions between the high-spin and low-spin electronic configurations at ∼235 K and 159 K, respectively. In contrast, weaker intermolecular interactions in 1 result in a gradual spin crossover above 300 K, with the maximum fraction of the HS state ∼25% achieved at 400 K. Complexes 2 and 3·2(3tpH) exhibit light-induced excited spin state trapping (LIESST) under irradiation with white light or a 532 nm laser at 5 K. After the photoexcitation, the trapped metastable HS state relaxes to the ground LS state with the average relaxation temperature of 81 K and 68 K, respectively. Examination of the relaxation dynamics by optical absorption spectroscopy on a single crystal of 3·2(3tpH) revealed the sigmoidal shape of the relaxation curves at lower temperatures, attributed to cooperative effects, as well as a plateau at ∼10% of the HS fraction at intermediate temperatures, hinting at a more complex mechanism for the relaxation of the LIESST phase in this material.

2.
J Am Chem Soc ; 146(21): 14620-14632, 2024 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-38743819

RESUMO

Metal phthalocyanines, a highly versatile class of aromatic, planar, macrocyclic molecules with a chelated central metal ion, are topical objects of ongoing research and particularly interesting due to their magnetic properties. However, while the current focus lies almost exclusively on spin-Zeeman-related effects, the high symmetry of the molecule and its circular shape suggests the exploitation of light-induced excitation of 2-fold degenerate vibrational states in order to generate, switch, and manipulate magnetic fields at the nanoscale. The underlying mechanism is a molecular pseudorotation that can be triggered by infrared pulses and gives rise to a quantized, small, but controllable magnetic dipole moment. We investigate the optical stimulation of vibrationally induced molecular magnetism and estimate changes in the magnetic shielding constants for confirmation by future experiments.

3.
Chemistry ; 30(42): e202401413, 2024 Jul 25.
Artigo em Inglês | MEDLINE | ID: mdl-38770893

RESUMO

A homologous series of 4,7-bis(aryl) substituted benzothiadiazole (BTD) compounds, containing the helicenic derivatives bis([4]helicene), bis([5]helicene) and bis([6]helicene), have been prepared upon a double Suzuki coupling between 3,6-bis(pinacolyl-borane)-BTD and the corresponding bromo-aryl precursors. The single crystal X-ray structure of the bis([4]helicene) compound shows the existence of both helicities (M) and (P) on the same molecule. All the compounds of the series are highly emissive in solution, with quantum yields of the emission ranging from 50 to 91 %. The enantiopure compounds (M,M) and (P,P) for the BTD-bis([6]helicene) have been prepared from the corresponding enantiopure 2-bromo-[6]helicene precursors. Their chiroptical properties have been investigated in correlation with density functional theory (DFT) calculations, which allowed to confidently assign the absolute configuration of the helicene arms and to characterize the different electronic transitions, including the low energy charge transfer excitation from helicenes to BTD. The enantiomerically pure fluorophores (M,M)- and (P,P)-BTD-bis([6]helicene), which exist in solution as two main conformers, according to the DFT calculations, show CPL activity in solution, with glum factors of ≈1.7×10-3 at λem=525 nm, and also in the solid state, with glum factors of ≈1.2×10-3 in spite of the strong decrease of the quantum efficiency.

4.
Xenotransplantation ; 31(2): e12858, 2024.
Artigo em Inglês | MEDLINE | ID: mdl-38646921

RESUMO

One of the prerequisites for successful organ xenotransplantation is a reasonable size match between the porcine organ and the recipient's organ to be replaced. Therefore, the selection of a suitable genetic background of source pigs is important. In this study, we investigated body and organ growth, cardiac function, and genetic diversity of a colony of Auckland Island pigs established at the Center for Innovative Medical Models (CiMM), LMU Munich. Male and female Auckland Island pig kidney cells (selected to be free of porcine endogenous retrovirus C) were imported from New Zealand, and founder animals were established by somatic cell nuclear transfer (SCNT). Morphologically, Auckland Island pigs have smaller body stature compared to many domestic pig breeds, rendering their organ dimensions well-suited for human transplantation. Furthermore, echocardiography assessments of Auckland Island pig hearts indicated normal structure and functioning across various age groups throughout the study. Single nucleotide polymorphism (SNP) analysis revealed higher runs of homozygosity (ROH) in Auckland Island pigs compared to other domestic pig breeds and demonstrated that the entire locus coding the swine leukocyte antigens (SLAs) was homozygous. Based on these findings, Auckland Island pigs represent a promising genetic background for organ xenotransplantation.


Assuntos
Variação Genética , Suínos , Transplante Heterólogo , Nova Zelândia , Suínos/genética , Animais , Masculino , Feminino , Humanos , Coração/anatomia & histologia , Coração/diagnóstico por imagem , Ecocardiografia , Genótipo , Homozigoto
5.
Nat Comput Sci ; 4(3): 163-164, 2024 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-38467871
6.
Gastric Cancer ; 27(1): 72-85, 2024 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-37874427

RESUMO

BACKGROUND: Recently, we presented Stroma AReactive Invasion Front Areas (SARIFA) as a new histomorphologic negative prognostic biomarker in gastric cancer. It is defined as direct contact between tumor cells and fat cells. The aim of this study was to further elucidate the underlying genomic, transcriptional, and immunological mechanisms of the SARIFA phenomenon. METHODS: To address these questions, SARIFA was classified on H&E-stained tissue sections of three cohorts: an external cohort (n = 489, prognostic validation), the TCGA-STAD cohort (n = 194, genomic and transcriptomic analysis), and a local cohort (n = 60, digital spatial profiling (whole transcriptome) and double RNA in situ hybridization/immunostaining of cytokines). RESULTS: SARIFA status proved to be an independent negative prognostic factor for overall survival in an external cohort of gastric carcinomas. In TCGA-STAD cohort, SARIFA is not driven by distinct genomic alterations, whereas the gene expression analyses showed an upregulation of FABP4 in SARIFA-positive tumors. In addition, the transcriptional regulations of white adipocyte differentiation, triglyceride metabolism, and catabolism were upregulated in pathway analyses. In the DSP analysis of SARIFA-positive tumors, FABP4 and the transcriptional regulation of white adipocyte differentiation were upregulated in macrophages. Additionally, a significantly lower expression of the cytokines IL6 and TNFα was observed at the invasion front. CONCLUSIONS: SARIFA proves to be a strong negative prognostic biomarker in advanced gastric cancer, implicating an interaction of tumor cells with tumor-promoting adipocytes with crucial changes in tumor cell metabolism. SARIFA is not driven by tumor genetics but is very likely driven by an altered immune response as a causative mechanism.


Assuntos
Carcinoma , Neoplasias Gástricas , Humanos , Prognóstico , Neoplasias Gástricas/patologia , Adipócitos/metabolismo , Adipócitos/patologia , Citocinas/metabolismo , Biomarcadores
7.
Chem Sci ; 14(44): 12715-12722, 2023 Nov 15.
Artigo em Inglês | MEDLINE | ID: mdl-38020370

RESUMO

In fused donor-acceptor (D-A) ensembles, rapid charge recombination often occurs because the D and A units are spatially close and strongly coupled. To the best of our knowledge, a long-lived charge separated (CS) state is still elusive in such systems. The results presented here show that symmetric annulation of two tetrathiafulvalene (TTF) donors to a central tetraazapyrene (TAP) acceptor via two quinoxaline units leads to a CS state lifetime of a few ns. A detailed study of the electronic interactions between TTF and TAP units in the ground and excited states was performed and compared with the asymmetric counterpart by cyclic voltammetry, optical absorption and ultrafast transient absorption spectroscopy. The results demonstrate that the photoinduced asymmetric charge trapping between two TTFs significantly stabilizes the CS state, which is also verified theoretically.

8.
J Chem Phys ; 159(1)2023 Jul 07.
Artigo em Inglês | MEDLINE | ID: mdl-37417752

RESUMO

The theoretical investigation of gas adsorption, storage, separation, diffusion, and related transport processes in porous materials relies on a detailed knowledge of the potential energy surface of molecules in a stationary environment. In this article, a new algorithm is presented, specifically developed for gas transport phenomena, which allows for a highly cost-effective determination of molecular potential energy surfaces. It is based on a symmetry-enhanced version of Gaussian process regression with embedded gradient information and employs an active learning strategy to keep the number of single point evaluations as low as possible. The performance of the algorithm is tested for a selection of gas sieving scenarios on porous, N-functionalized graphene and for the intermolecular interaction of CH4 and N2.


Assuntos
Algoritmos , Porosidade , Adsorção , Transporte Biológico , Difusão
9.
Chemistry ; 29(49): e202301517, 2023 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-37204268

RESUMO

Sub-nanometer metal clusters have special physical and chemical properties, significantly different from those of nanoparticles. However, there is a major concern about their thermal stability and susceptibility to oxidation. In situ X-ray Absorption spectroscopy and Near Ambient Pressure X-ray Photoelectron spectroscopy results reveal that supported Cu5 clusters are resistant to irreversible oxidation at least up to 773 K, even in the presence of 0.15 mbar of oxygen. These experimental findings can be formally described by a theoretical model which combines dispersion-corrected DFT and first principles thermochemistry revealing that most of the adsorbed O2 molecules are transformed into superoxo and peroxo species by an interplay of collective charge transfer within the network of Cu atoms and large amplitude "breathing" motions. A chemical phase diagram for Cu oxidation states of the Cu5 -oxygen system is presented, clearly different from the already known bulk and nano-structured chemistry of Cu.

11.
J Dairy Sci ; 106(3): 1925-1941, 2023 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-36710189

RESUMO

Although the quantitative trait locus (QTL) on chromosome 18 (BTA18) associated with paternal calving ease and stillbirth in Holstein Friesian cattle and its cross has been known for over 20 years, to our knowledge, the exact causal genetic sequence has yet escaped identification. The aim of this study was to re-examine the region of the published QTL on BTA18 and to investigate the possible reasons behind this elusiveness. For this purpose, we carried out a combined linkage disequilibrium and linkage analysis using genotyping data of 2,697 German Holstein Friesian (HF) animals and subsequent whole-genome sequencing (WGS) data analyses and genome assembly of HF samples. We confirmed the known QTL in the 95% confidence interval of 1.089 Mbp between 58.34 and 59.43 Mbp on BTA18. Additionally, these 4 SNPs in the near-perfect linkage disequilibrium with the QTL haplotype were identified: rs381577268 (on 57,816,137 bp, C/T), rs381878735 (on 59,574,329 bp, A/T), rs464221818 (on 59,329,176 bp, C/T), and rs472502785 (on 59,345,689 bp, T/C). Search for the causal mutation using short and long-read sequences, and methylation data of the BTA18 QTL region did not reveal any candidates though. The assembly showed problems in the region, as well as an abundance of segmental duplications within and around the region. Taking the QTL of BTA18 in Holstein cattle as an example, the data presented in this study comprehensively characterize the genomic features that could also be relevant for other such elusive QTL in various other cattle breeds and livestock species as well.


Assuntos
Cromossomos , Locos de Características Quantitativas , Bovinos , Animais , Fenótipo , Desequilíbrio de Ligação , Genômica , Polimorfismo de Nucleotídeo Único
12.
Faraday Discuss ; 242(0): 160-173, 2023 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-36178317

RESUMO

Nanoparticles with diameters in the range of a few nanometers, consisting of gold and vanadium oxide, are synthesized by sequential doping of cold helium droplets in a molecular beam apparatus and deposited on solid carbon substrates. After surface deposition, the samples are removed and various measurement techniques are applied to characterize the created particles: scanning transmission electron microscopy (STEM) at atomic resolution, temperature dependent STEM and TEM up to 650 °C, energy-dispersive X-ray spectroscopy (EDXS) and electron energy loss spectroscopy (EELS). In previous experiments we have shown that pure V2O5 nanoparticles can be generated by sublimation from the bulk and deposited without affecting their original stoichiometry. Interestingly, our follow-up attempts to create Au@V2O5 core@shell particles do not yield the expected encapsulated structure. Instead, Janus particles of Au and V2O5 with diameters between 10 and 20 nm are identified after deposition. At the interface of the Au and the V2O5 parts we observe an epitaxial-like growth of the vanadium oxide next to the Au structure. To test the temperature stability of these Janus-type particles, the samples are heated in situ during the STEM measurements from room temperature up to 650 °C, where a reduction from V2O5 to V2O3 is followed by a restructuring of the gold atoms to form a Wulff-shaped cluster layer. The temperature dependent dynamic interplay between gold and vanadium oxide in structures of only a few nanometer size is the central topic of this contribution to the Faraday Discussion.

13.
J Phys Chem A ; 126(36): 6221-6235, 2022 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-36067495

RESUMO

Using the supramolecular approach developed for the study of the guest-host interactions in the zeolite Y encapsulated [Fe(bpy)3]2+ compound: [Fe(bpy)3]2+@Y (bpy = 2,2'-bipyridine) [Vargas et al., J. Chem. Theory Comput. 2009, 5, 97-115], we apply density functional theory (DFT) to the study of the influence of zeolite Y encapsulation on the structural and energetic properties of [Co(bpy)3]2+ in the low-spin (LS) and high-spin (HS) states, while revisiting [Fe(bpy)3]2+@Y. Although the accurate prediction of the HS-LS energy difference ΔEHLel remains challenging for current DFT methods, they give accurate estimates of its variation Δ(ΔEHLel) in a series of complexes of a given transition metal ion. Therefore, denoting [M(bpy)3]2+@YSM as the supramolecular model of the inclusion compounds, the values of ΔEHLel for the bpy complexes in the gas phase and in the supercage of zeolite Y were determined by combining the DFT estimates of Δ(ΔEHLel) in the series {[M(NCH)6]2+, [M(bpy)3]2+, and [M(bpy)3]2+@YSM}, with accurate CCSD(T) estimates of ΔEHLel in the benchmark complexes [M(NCH)6]2+ (M = Fe, Co) [Lawson Daku et al., J. Chem. Theory Comput., 2012, 8, 4216-4231]. Generalized gradient approximations as well as global and range-separated hybrids were employed. In order to better account for the key role of dispersion, they were also augmented with the semiempirical D2, D3BJ, and D3BJM dispersion corrections when available. The use of the D3BJ and D3BJM corrections led to similar results, and this is only with the use of the D2 scheme that (i) the free and encapsulated [Fe(bpy)3]2+ are correctly predicted as LS species and that (ii) the encapsulation of both complexes translates into a destabilization of their HS state with respect to their LS state. The increase of the HS-LS energy difference is smaller for [Co(bpy)3]2+ than [Fe(bpy)3]2+ because the HS-LS molecular volume difference ΔVHL in [Co(bpy)3]2+ is ∼50% smaller than in [Fe(bpy)3]2+. Periodic DFT calculations performed on crystalline [M(bpy)3]2+@Y show that the employed [M(bpy)3]2+@YSM supramolecular model allows the influence of encapsulation on the geometry and the spin-state energetics of [M(bpy)3]2+ (M = Fe, Co) to be quantitatively captured.

14.
J Phys Chem A ; 126(10): 1674-1680, 2022 Mar 17.
Artigo em Inglês | MEDLINE | ID: mdl-35258966

RESUMO

In the year 1933, Herzberg and Teller realized that the potential energy surface of a triatomic, linear molecule splits into two as soon as the molecule is bent. The phenomenon, later dubbed the Renner-Teller effect due to the detailed follow-up work of Renner on the subject, describes the coupling of a symmetry-reducing molecular vibration with degenerate electronic states. In this article, we show that a very similar type of nonadiabatic coupling can occur for certain translational degrees of freedom of diatomic, electronically degenerate molecules when trapped in a nearly spherical or cylindrical quantum confinement, e.g., realized through electromagnetic fields or molecular encapsulation. We illustrate this on the example of fullerene-encapsulated nitric oxide, and provide a prediction of its interesting, perturbed vibronic spectrum.

15.
Phys Chem Chem Phys ; 24(2): 982-994, 2022 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-34918013

RESUMO

The thermal spin transition and the photo-induced high-spin → low-spin relaxation of the prototypical [Fe(ptz)6](BF4)2 spin-crossover compound (ptz = 1-propyltetrazole) diluted in the isostructural ruthenium host lattice [Ru(ptz)6](BF4)2, which stabilizes the Fe(II) low-spin state, have been investigated. We demonstrate the presence of a crystallographic phase transition around 145 K (i.e. from the high-temperature ordered high-spin phase to a low-temperature disordered low-spin phase) upon slow cooling from room temperature. This crystallographic phase transition is decoupled from the thermal spin transition. A supercooled ordered low-spin phase is observed as in the pure Fe(II) analogue upon fast cooling. A similar order-disorder phase transition is also observed for pure [Ru(ptz)6](BF4)2 but at relatively higher temperature (i.e. at around 150 K) without involving any spin transition. For Ru-diluted [Fe(ptz)6]2+, the crystallographic phase transition as well as strong cooperative effects involving various degrees of elastic frustration are at the origin of stepped sigmoidal high-spin → low-spin relaxation curves, which are modelled in the framework of a classical mean field model, considering both the tunnelling and thermally activated regimes. Optical microscopy studies performed on two different single crystals showed the existence of hysteretic thermal transitions with slight domain formation, hardly visible in the static crystal images. This behavior is attributed to the double effect upon Ru dilution, which decreases the cooperative character of the transition and simultaneously reduces the optical contrast between the LS and HS states. Moreover, the transition temperature revealed to be slightly crystal dependent, highlighting the crucial role of the spatial distribution of Ru from one crystal to another, in addition to the well-known effects of crystal shape and size.

16.
Molecules ; 26(19)2021 Sep 24.
Artigo em Inglês | MEDLINE | ID: mdl-34641327

RESUMO

We present path integral molecular dynamics (PIMD) calculations of an electron transfer from a heliophobic Cs2 dimer in its (3Σu) state, located on the surface of a He droplet, to a heliophilic, fully immersed C60 molecule. Supported by electron ionization mass spectroscopy measurements (Renzler et al., J. Chem. Phys.2016, 145, 181101), this spatially quenched reaction was characterized as a harpoon-type or long-range electron transfer in a previous high-level ab initio study (de Lara-Castells et al., J. Phys. Chem. Lett.2017, 8, 4284). To go beyond the static approach, classical and quantum PIMD simulations are performed at 2 K, slightly below the critical temperature for helium superfluidity (2.172 K). Calculations are executed in the NVT ensemble as well as the NVE ensemble to provide insights into real-time dynamics. A droplet size of 2090 atoms is assumed to study the impact of spatial hindrance on reactivity. By changing the number of beads in the PIMD simulations, the impact of quantization can be studied in greater detail and without an implicit assumption of superfluidity. We find that the reaction probability increases with higher levels of quantization. Our findings confirm earlier, static predictions of a rotational motion of the Cs2 dimer upon reacting with the fullerene, involving a substantial displacement of helium. However, it also raises the new question of whether the interacting species are driven out-of-equilibrium after impurity uptake, since reactivity is strongly quenched if a full thermal equilibration is assumed. More generally, our work points towards a novel mechanism for long-range electron transfer through an interplay between nuclear quantum delocalization within the confining medium and delocalized electronic dispersion forces acting on the two reactants.

17.
J Phys Chem A ; 125(41): 9143-9150, 2021 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-34633823

RESUMO

The electronic structure of subnanometric clusters, far off the bulk regime, is still dominated by molecular characteristics. The spatial arrangement of the notoriously undercoordinated metal atoms is strongly coupled to the electronic properties of the system, which makes this class of materials particularly interesting for applications including luminescence, sensing, bioimaging, theranostics, energy conversion, catalysis, and photocatalysis. Opposing a common rule of thumb that assumes an increasing chemical reactivity with smaller cluster size, Cu5 clusters have proven to be exceptionally resistant to irreversible oxidation, i.e., the dissociative chemisorption of molecular oxygen. Besides providing reasons for this behavior in the case of heavy loading with molecular oxygen, we investigate the competition between physisorption and molecular chemisorption from the perspective of nonadiabatic effects. Landau-Zener theory is applied to the Cu5(O2)3 complex to estimate the probability for a switching between the electronic states correlating the neutral O2 + Cu5(O2)2 and the ionic O2- + (Cu5(O2)2)+ fragments in a diabatic representation. Our work demonstrates the involvement of strong nonadiabatic effects in the associated charge transfer process, which might be a common motive in reactions involving subnanometric metal structures.

18.
Mol Ecol ; 30(24): 6701-6717, 2021 12.
Artigo em Inglês | MEDLINE | ID: mdl-34534381

RESUMO

To predict species responses to anthropogenic disturbances and climate change, it is reasonable to use species with high sensitivity to such factors. Snow sheep (Ovis nivicola) could represent a good candidate for this; as the only large herbivore species adapted to the cold and alpine habitats of northeastern Siberia, it plays a crucial role in its ecosystem. Despite having an extensive geographical distribution among all ovine species, it is one of the least studied. In this study, we sequenced and analysed six genomes of snow sheep in combination with all other wild sheep species to infer key aspects of their evolutionary history and unveil the genetic basis of their adaptation to subarctic environments. Despite their large census population size, snow sheep genomes showed remarkably low heterozygosity, which could reflect the effect of isolation and historical bottlenecks that we inferred using the pairwise sequential Markovian coalescent and runs of homozygosity. F4 -statistics indicated instances of introgression involving snow sheep with argali (Ovis ammon) and Dall (Ovis dalli) sheep, suggesting that these species might have been more widespread during the Pleistocene. Furthermore, the introgressed segments, which were identified using mainly minimum relative node depth, covered genes associated with immunity, adipogenesis and morphology-related traits, representing potential targets of adaptive introgression. Genes related to mitochondrial functions and thermogenesis associated with adipose tissue were identified to be under selection. Overall, our data suggest introgression as a mechanism facilitating adaptation in wild sheep species and provide insights into the genetic mechanisms underlying cold adaptation in snow sheep.


Assuntos
Efeitos Antropogênicos , Ecossistema , Aclimatação/genética , Animais , Genoma , Ovinos/genética , Sequenciamento Completo do Genoma
19.
Genome Biol ; 22(1): 225, 2021 08 16.
Artigo em Inglês | MEDLINE | ID: mdl-34399815

RESUMO

BACKGROUND: Retrotransposons are genetic elements inducing mutations in all domains of life. Despite their detrimental effect, retrotransposons can become temporarily active during epigenetic reprogramming and cellular stress response, which may accelerate host genome evolution. In fungal pathogens, a positive role has been attributed to retrotransposons when shaping genome architecture and expression of genes encoding pathogenicity factors; thus, retrotransposons are known to influence pathogenicity. RESULTS: We uncover a hitherto unknown role of fungal retrotransposons as being pathogenicity factors, themselves. The aggressive fungal plant pathogen, Botrytis cinerea, is known to deliver some long-terminal repeat (LTR) deriving regulatory trans-species small RNAs (BcsRNAs) into plant cells to suppress host gene expression for infection. We find that naturally occurring, less aggressive B. cinerea strains possess considerably lower copy numbers of LTR retrotransposons and had lost retrotransposon BcsRNA production. Using a transgenic proof-of-concept approach, we reconstitute retrotransposon expression in a BcsRNA-lacking B. cinerea strain, which results in enhanced aggressiveness in a retrotransposon and BcsRNA expression-dependent manner. Moreover, retrotransposon expression in B. cinerea leads to suppression of plant defence-related genes during infection. CONCLUSIONS: We propose that retrotransposons are pathogenicity factors that manipulate host plant gene expression by encoding trans-species BcsRNAs. Taken together, the novelty that retrotransposons are pathogenicity factors will have a broad impact on studies of host-microbe interactions and pathology.


Assuntos
Botrytis/genética , Plantas/genética , Retroelementos , Fatores de Virulência , Proteínas Fúngicas/genética , Expressão Gênica , Genes de Plantas , Interações Hospedeiro-Patógeno/genética , Doenças das Plantas/microbiologia , Plantas/microbiologia , RNA-Seq , Sequências Repetidas Terminais , Sequenciamento Completo do Genoma
20.
Front Chem ; 9: 721272, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-34368088

RESUMO

A series of bis(triphenylamine)benzodifuran chromophores have been synthesized and fully characterised. Starting from suitably functionalized benzodifuran (BDF) precursors, two triphenylamine (TPA) moieties are symmetrically coupled to a central BDF unit either at 4,8-positions through double bonds (1) and single bonds (2) respectively, or at 2,6-positions through double bonds (3). Their electronic absorption and photoluminescence properties as well as redox behaviour have been investigated in detail, indicating that the π-extended conjugation via vinyl linkers in 1 and 3 leads to comparatively strong electronic interactions between the relevant redox moieties TPA and BDF. Due to intriguing electronic properties and structural planarity, 3a has been applied as a dopant emitter in organic light-emitting diodes. A yellowish-green OLED exhibits a high external quantum efficiency (EQE) of 6.2%, thus exceeding the theoretical upper limit most likely due to energy transfer from an interface exciplex to an emissive layer and/or favorable horizontal orientation.

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