Photoinduced behaviour of N,N-bidentate manganese(I) and rhenium(I) tricarbonyl complexes for singlet oxygen generation and CO release.

The combined action of singlet oxygen (1O2) and photoinduced carbon monoxide (CO) released by tricarbonyl metal complexes is a promising synergic treatment against multi-resistant bacterial infections. In this work, we explore the use of a polydentate ligand (bpm = 2,2-bipyrimidine) that offers the opportunity to accommodate two metal centers exhibiting both singlet oxygen generation and carbon monoxide releasing properties in a single molecule. A series of monometallic ([(bpm)M(CO)3Br]; M = Mn, Re) and homo or hetero bimetallic ([Br(CO)3M(bpm)M'(CO)3Br]; M = Mn, Re) compounds were synthesized in moderate to good yields by modulating the metal precursor or the stoichiometry, also the syn:anti isomers ratio for the bimetallic complexes was dependent on the experimental conditions used. DFT modelling shows the anti-isomer is more stable than the syn-isomer by less than 8 kJ mol-1, which is consistent with those experimentally observed in terms of majority product and the effect of experimental conditions over the anti-syn ratio. The HOMO-LUMO gap is lower for the mono and bimetallic rhenium(I) compounds compared to the values for the manganese(I) analogues, while the heterometallic complex shows intermediate values for the anti-isomer. The photophysical characterization shows typical absorption and emission bands with MLCT character. In addition, CO-release and 1O2 generation quantum yields were evaluated for the monometallic Mnbpm and Rebpm homologues and compared with values obtained for the homo- and hetero-bimetallic complexes. Interestingly the replacement of a Mn(CO)3Br moiety in MnbpmMn by a Re(CO)3Br one makes the heterometallic MnbpmRe molecule a molecular oxygen sensitizer and partially retaining its carbon monoxide releasing ability.

Postoperative Morbidity and Interstage Hemodynamics Following Stage I Palliation in Patients with Turner Syndrome and Hypoplastic Left Heart Syndrome.

BACKGROUND: Turner syndrome (TS) is associated with left-sided cardiac lesions, including hypoplastic left heart syndrome (HLHS). Mortality as high as 80-90% has been reported following stage I single-ventricle palliation (S1P) in patients with TS and HLHS (TS + HLHS). The specific factors that relate to poor outcomes are not well understood. METHODS: This is a single-center, retrospective cohort study that includes 197 patients with HLHS who underwent S1P between 2008 and 2022. The clinical outcomes and interstage hemodynamics of TS + HLHS patients (N = 11) were compared with HLHS without TS (TS-HLHS), (N = 186). RESULTS: Of the 11 TS + HLHS patients, 10 underwent S1P; 4 underwent Glenn and 1 had hemodynamics considered prohibitive for Glenn; only 1 survived to Fontan palliation. Post-S1P mortality was higher in TS + HLHS (60 v 25%, p = 0.017). Following S1P, TS + HLHS had higher rates of postoperative ECMO (70 v 28%, p = 0.006), surgical necrotizing enterocolitis (20 v 3%, p = 0.007), peritoneal drain placement (70 v 31%, p = 0.012), urinary tract infection (30 v 9%, p = 0.035), and ICU readmissions (median 5 v 1, p = 0.035). Interstage hemodynamics demonstrated higher right ventricular end diastolic, (11 v 8mmHg, p = 0.033), mean pulmonary artery (20 v 13mmHg) (p = 0.002), and left atrial pressures (9 v 6mmHg, p = 0.047) in TS + HLHS. CONCLUSION: High mortality rates are described in TS + HLHS patients following S1P. In our cohort, despite most surviving more than 30 days post-S1P, long-term survival remained poor. Interstage catheterization data suggest poor physiologic candidacy for subsequent stages of single-ventricle palliation. Understanding the clinical and hemodynamic factors related to poor outcomes in TS + HLHS will help inform management for this population.

Sexual signal evolution and patterns of assortative mating across an intraspecific contact zone.

Contact zones provide important insights into the evolutionary processes that underlie lineage divergence and speciation. Here, we use a contact zone to ascertain speciation potential in the red-eyed treefrog (Agalychnis callidryas), a brightly coloured and polymorphic frog that exhibits unusually high levels of intraspecific variation. Populations of A. callidryas differ in a number of traits, several of which are known sexual signals that mediate premating reproductive isolation in allopatric populations. Along the Caribbean coast of Costa Rica, a ~100 km contact zone, situated between two phenotypically and genetically divergent parent populations, contains multiple colour pattern phenotypes and late-generation hybrids. This contact zone provides the opportunity to examine processes that are important in the earliest stages of lineage divergence. We performed analyses of colour pattern variation in five contact zone sites and six parental sites and found complex, continuous colour variation along the contact zone. We found discordance between the geographic distribution of colour pattern and previously described genomic population structure. We then used a parental site and contact zone site to measure assortative mating and directional selection from naturally-occurring amplectant mating pairs. We found assortative mating in a parental population, but no assortative mating in the contact zone. Furthermore, we uncovered evidence of directional preference towards the adjacent parental phenotype in the contact zone population, but no directional preference in the parent population. Combined, these data provide insights into potential dynamics at the contact zone borders and indicate that incipient speciation between parent populations will be slowed.

Quantum ghost imaging based on a "looking back" 2D SPAD array.

Quantum ghost imaging (QGI) is an intriguing imaging protocol that exploits photon-pair correlations stemming from spontaneous parametric down-conversion (SPDC). QGI retrieves images from two-path joint measurements, where single-path detection does not allow us to reconstruct the target image. Here we report on a QGI implementation exploiting a two-dimensional (2D) single-photon avalanche diode (SPAD) array detector for the spatially resolving path. Moreover, the employment of non-degenerate SPDC allows us to investigate samples at infrared wavelengths without the need for short-wave infrared (SWIR) cameras, while the spatial detection can be still performed in the visible region, where the more advanced silicon-based technology can be exploited. Our findings advance QGI schemes towards practical applications.

Genotype Prevalence of Lactose Deficiency, Vitamin D Deficiency, and the Vitamin D Receptor in a Chilean Inflammatory Bowel Disease Cohort: Insights from an Observational Study.

Lactose intolerance (LI) and vitamin D deficiency (VDD) have been linked to inflammatory bowel disease (IBD). We conducted an observational study in 192 Chilean IBD patients to investigate the prevalence of a specific gene variant (LCT-13910 CC genotype) associated with LI and the prevalence of VDD/Vitamin D Receptor (VDR) gene variants. Blood samples were analyzed using Illumina's Infinium Global Screening Array. The LCT-13910 CC genotype was found in 61% of IBD patients, similar to Chilean Hispanic controls and lower than Chilean Amerindian controls. The frequency of the LCT-13910-C allele in Chilean IBD patients (0.79) was comparable to the general population and higher than Europeans (0.49). Regarding VDR and VDD variants, in our study, the rs12785878-GG variant was associated with an increased risk of IBD (OR = 2.64, CI = 1.61-4.32; p-value = 0.001). Sixty-one percent of the Chilean IBD cohort have a genetic predisposition to lactose malabsorption, and a significant proportion exhibit genetic variants associated with VDD/VDR. Screening for LI and VDD is crucial in this Latin American IBD population.

Nicotine Exposure in a Phencyclidine-Induced Mice Model of Schizophrenia: Sex-Selective Medial Prefrontal Cortex Protein Markers of the Combined Insults in Adolescent Mice.

Tobacco misuse as a comorbidity of schizophrenia is frequently established during adolescence. However, comorbidity markers are still missing. Here, the method of label-free proteomics was used to identify deregulated proteins in the medial prefrontal cortex (prelimbic and infralimbic) of male and female mice modelled to schizophrenia with a history of nicotine exposure during adolescence. Phencyclidine (PCP), used to model schizophrenia (SCHZ), was combined with an established model of nicotine minipump infusions (NIC). The combined insults led to worse outcomes than each insult separately when considering the absolute number of deregulated proteins and that of exclusively deregulated ones. Partially shared Reactome pathways between sexes and between PCP, NIC and PCPNIC groups indicate functional overlaps. Distinctively, proteins differentially expressed exclusively in PCPNIC mice reveal unique effects associated with the comorbidity model. Interactome maps of these proteins identified sex-selective subnetworks, within which some proteins stood out: for females, peptidyl-prolyl cis-trans isomerase (Fkbp1a) and heat shock 70 kDa protein 1B (Hspa1b), both components of the oxidative stress subnetwork, and gamma-enolase (Eno2), a component of the energy metabolism subnetwork; and for males, amphiphysin (Amph), a component of the synaptic transmission subnetwork. These are proposed to be further investigated and validated as markers of the combined insult during adolescence.

Genetic isolation by distance underlies colour pattern divergence in red-eyed treefrogs (Agalychnis callidryas).

Investigating the spatial distribution of genetic and phenotypic variation can provide insights into the evolutionary processes that shape diversity in natural systems. We characterized patterns of genetic and phenotypic diversity to learn about drivers of colour-pattern diversification in red-eyed treefrogs (Agalychnis callidryas) in Costa Rica. Along the Pacific coast, red-eyed treefrogs have conspicuous leg colour patterning that transitions from orange in the north to purple in the south. We measured phenotypic variation of frogs, with increased sampling at sites where the orange-to-purple transition occurs. At the transition zone, we discovered the co-occurrence of multiple colour-pattern morphs. To explore possible causes of this variation, we generated a single nucleotide polymorphism data set to analyse population genetic structure, measure genetic diversity and infer the processes that mediate genotype-phenotype dynamics. We investigated how patterns of genetic relatedness correspond to individual measures of colour pattern along the coast, including testing for the role of hybridization in geographic regions where orange and purple phenotypic groups co-occur. We found no evidence that colour-pattern polymorphism in the transition zone arose through recent hybridization. Instead, a strong pattern of genetic isolation by distance indicates that colour-pattern variation was either retained through other processes such as ancestral colour polymorphisms or ancient secondary contact, or else it was generated by novel mutations. We found that phenotype changes along the Pacific coast more than would be expected based on genetic divergence and geographic distance alone. Combined, our results suggest the possibility of selective pressures acting on colour pattern at a small geographic scale.

La investigación de la distribución espacial de la variación genética y fenotípica puede proporcionar información sobre los procesos evolutivos que dan forma a la diversidad en los sistemas naturales. Caracterizamos patrones de diversidad genética y fenotípica para conocer los impulsores de la diversificación de patrones de color en ranas con ojos rojos (Agalychnis callidryas) en Costa Rica. A lo largo de la costa del Pacífico, las ranas con ojos rojos tienen un patrón de color llamativo en las patas que cambia de naranja en el norte a púrpura en el sur. Medimos la variación fenotípica de las ranas en los sitios del Pacífico, con un mayor muestreo en los sitios donde ocurre la transición de naranja a púrpura. En la zona de transición, descubrimos la co-ocurrencia de múltiples morfos de patrones de color. Para explorar las posibles causas de esta variación, generamos un conjunto de datos SNP con secuenciación RAD para analizar la estructura genética de la población, medir la diversidad genética e inferir los procesos que median la dinámica genotipo-fenotipo. Investigamos cómo los patrones de parentesco genético se corresponden con medidas individuales de patrón de color a lo largo de la costa, incluidas las pruebas del papel de la hibridación en regiones geográficas donde coexisten grupos fenotípicos naranja y morado. No encontramos evidencia de que el polimorfismo del patrón de color en la zona de transición surgiera a través de una hibridación o introgresión reciente. En cambio, un fuerte patrón de aislamiento genético por distancia indica que la variación del patrón de color se retuvo a través de otros procesos, como los polimorfismos de color ancestrales, el contacto secundario antiguo o la generada por mutaciones novedosas. Descubrimos que el fenotipo de color cambia a lo largo de la costa del Pacífico más de lo que se esperaría solo por la divergencia genética y la distancia geográfica. Combinados, nuestros resultados sugieren la posibilidad de que las presiones selectivas actúen sobre el patrón de color a pequeña escala geográfica.

Structure and excited-state dynamics of dimeric copper(i) photosensitizers investigated by time-resolved X-ray and optical transient absorption spectroscopy.

Time-resolved X-ray (tr-XAS) and optical transient absorption (OTA) spectroscopy in the picosecond time scale coupled with Density Functional theory (DFT) and X-ray absorption near-edge structure (XANES) calculations are applied to study three homoleptic Cu(i) dimeric chromophores with ethyl and longer propyl spacers, denoted as [Cu2(mphenet)2]Cl2 (C1), [Cu2(mphenet)2](ClO4)2 (C2) and [Cu2(mphenpr)2](ClO4)2 (C3) (where mphenet = 1,2-bis(9-methyl-1,10-phenanthrolin-2-yl)ethane and mphenpr = 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane). Tr-XAS analysis after light illumination at ∼ 100 ps illustrate the formation of a flattened triplet excited state in all 3 complexes. Optical transient absorption (OTA) analysis for C1 monitored in water and C2 and C3 measured in acetonitrile reveals distinct excited-state lifetimes of 169 ps, 670 ps and 1600 ps respectively. These differences are associated to changes in the solvent (comparing C1 and C2) and the flexibility of the ligand to adapt after Cu flattening upon excitation (C2 and C3). Our results are important for the improved structural dynamics of these types of Cu-based dimeric compounds, and can guide the integration of these chromophores into more complex solar energy conversion schemes.

Genetic and phenotypic evidence of a contact zone between divergent colour morphs of the iconic red-eyed treefrog.

Hybrid zones act as natural laboratories where divergent genomes interact, providing powerful systems for examining the evolutionary processes underlying biological diversity. In this study, we characterized patterns of genomic and phenotypic variation resulting from hybridization between divergent intraspecific lineages of the Neotropical red-eyed treefrog (Agalychnis callidryas). We found genetic evidence of a newly discovered contact zone and phenotypic novelty in leg colour-a trait suspected to play a role in mediating assortative mating in this species. Analysis of hybrid ancestry revealed an abundance of later-generation Fn individuals, suggesting persistence of hybrids in the contact zone. Hybrids are predominantly of southern ancestry but are phenotypically more similar to northern populations. Genome-wide association mapping revealed QTL with measurable effects on leg-colour variation, but further work is required to dissect the architecture of this trait and establish causal links. Further, genomic cline analyses indicated substantial variation in patterns of introgression across the genome. Directional introgression of loci associated with different aspects of leg colour are inherited from each parental lineage, creating a distinct hybrid colour pattern. We show that hybridization can generate new phenotypes, revealing the evolutionary processes that potentially underlie patterns of phenotypic diversity in this iconic polytypic frog. Our study is consistent with a role of hybridization and sexual selection in lineage diversification, evolutionary processes that have been implicated in accelerating divergence in the most phenotypically diverse species.

Reactivity of CuIN4 Flattened Complexes: Interplay between Coordination Geometry and Ligand Flexibility.

The relation between redox activity and coordination geometry in CuIN4 complexes indicates that more flattened structures tend to be more reactive. Such a preorganization of the ligand confers to the complex geometries closer to a transition state, which has been termed the "entatic" state in metalloproteins, more recently extending this concept for copper complexes. However, many aspects of the redox chemistry of CuI complexes cannot be explained only by flattening. For instance, the role of ligand flexibility in this context is an open debate nowadays. To analyze this point, we studied oxidation properties of a series of five monometallic CuI Schiff-base complexes, [CuI(Ln)]+, which span a range of geometries from a distorted square planar (n = 3) to a distorted tetrahedron (n = 6, 7). This stepped control of the structure around the CuI atom allows us to explore the effect of the flattening distortion on both the electronic and redox properties through the series. Experimental studies were complemented by a theoretical analysis based on density functional theory calculations. As expected, oxidation was favored in the flattened structures, spanning a broad potential window of 370 mV for the complete series. This orderly behavior was tested in the reductive dehalogenation reaction of tetrachloroethane (TCE). Kinetic studies show that CuI oxidation by TCE is faster as the flattening distortion is higher and the oxidation potentials of the metal are lower. However, the most reactive complex was not the more planar, contradicting the trend expected from oxidation potentials. The origin of this irregularity is related to ligand flexibility and its connection with the atom/electron transfer reaction path, highlighting the need to consider effects beyond flattening distortion to better understand the reactivity of this important class of complexes.

Enhancement of Terbium(III)-Centered Luminescence by Tuning the Triplet Energy Level of Substituted Pyridylamino-4-R-Phenoxo Tripodal Ligands.

A series of luminescent phenoxo-bridged dinuclear TbIII complexes with tripodal ligands, 2,2'-[[(2-pyridinylmethyl)imino]di(methylene)]-bis(4-R-phenol), where R = CH3 (LCH3) (I), Cl (LCl) (II), CH3O (LCH3O) (III), COOCH3 (LCOOCH3) (IV), were prepared to probe the effect of para-substitution on the phenol ring of the ligand on the TbIII luminescence. For these TbIII complexes a complete suppression of the ligand-centered fluorescence is observed, which demonstrates an efficient ligand-to-metal energy transfer. Complex IV was found to be the one that shows the greater intensity of the emission at room temperature. The obtained quantum yields follow the trend IV > II ≫ I > III. The quantum yield for II and IV is approximately five times greater than those obtained for I and III, indicating that the LCl and LCOOCH3 are better sensitizers of the TbIII ions. These results were rationalized in terms of the variation of the energy gap between the triplet level (T1) of the ligand and the emissive 5D4 level of TbIII, due to the electron-acceptor or electron-donor properties of the substituents. The τav values are in the millisecond range for all the studied complexes and resulted independent of temperature. The Commission International d'Eclairage coordinates (CIE) for all complexes are in the green color region, being insensitive to the variation of temperature. Moreover, the color purity (CP) is ca. 90% for all complexes, being ca. 100% for IV. Thus, the introduction of electron-acceptor substituents on the ligand permitted us to improve the luminescent properties of the TbIII complexes.

Measured ammonia emissions from tropical and subtropical pastures: A comparison with 2006 IPCC, 2019 Refinement to the 2006 IPCC, and EMEP/EEA (European Monitoring and Evaluation Programme and European Environmental Agency) inventory estimates.

Agriculture is the largest source of ammonia (NH3) emissions. As NH3 is an indirect greenhouse gas, NH3 measurements are crucial to improving greenhouse gas emission inventory estimates. Moreover, NH3 emissions have wider implications for environmental and human health. Only a few studies have measured NH3 emissions from pastures in the tropics and subtropics and none has compared emissions to inventory estimates. The objectives of this study were to (1) measure NH3 emissions from dairy pastures in tropical and subtropical regions; (2) calculate NH3 emissions factors (EF) for each campaign; and (3) compare measured EF with those based on the 2006 Intergovernmental Panel on Climate Change (IPCC) Tier 1, 2019 Refinement to the 2006 IPCC Tier 1, and the European Monitoring and Evaluation Programme/European Environmental Agency (EMPE/EEA) Tier 2 inventory estimates. Pasture NH3 emissions were measured on 3 dairy farms in Costa Rica. On each dairy, NH3 emissions were measured twice during the wet season and once during the dry season using a micrometeorological integrated horizontal-flux mass-balance method. Emissions were measured from excreta (dung and urine) deposited by grazing cattle and the subsequent application of organic (slurry) or synthetic fertilizer (ammonium nitrate or urea). Measured EF for all campaigns [from grazing cattle excreta and any subsequent slurry or fertilizer application; 4.9 ± 0.9% of applied nitrogen (mean ± SE)] were similar to those of the EMEP/EEA Tier 2 approach (6.1 ± 0.9%; mean ± SE) and 4 times lower than 2006 IPCC and 2019 Refinement to 2006 IPCC Tier 1 default estimates (17.7 ± 1.4 and 18.2 ± 0.9%, respectively; mean ± SE). Measured EF for excreta deposited on pasture and excreta both deposited on pasture and slurry application [3.9 ± 2.1 and 4.2 ± 2.1% (mean ± 95% CI), respectively] were 5 times lower than default EF assumed by 2006 IPCC and 2019 Refinement to 2006 IPCC methodology (both 20 and 21%, respectively), whereas EMEP/EAA estimates were similar [6.0 and 4.6 ± 0.3% (mean ± 95% CI), respectively]. This suggests an overestimation of EF from excreta deposited on pasture and slurry applications in tropical and subtropical regions by IPCC methodologies. Furthermore, rainfall, which is not included as a parameter in the current EMEP/EEA Tier 2 methodology, appeared to reduce NH3 emissions, suggesting that accounting for this in the inventory methodologies could improve inventory estimates.

Tuning White Light Emission in Dinuclear Phenoxo Bridged DyIII Complexes.

A new series of dinuclear dysprosium(III) complexes, [Dy2(LCH3)2(NO3)2(MeOH)2] (I), [Dy2(LCH3)2(NO3)2(DMF)2]·2DMF (II), [Dy2(LCl)2(NO3)2(DMF)2]·2DMF (III), and [Dy2(LCH3O)2(NO3)2(DMF)2] (IV), with 2,2'-[[(2-pyridinylmethyl)imino]di(methylene)]bis(4-R-phenol), where R = CH3, Cl, and CH3O, were investigated as potential white light emitters. All octacoordinated dysprosium(III) are phenoxo-bridged species and have a similar coordination environment. Nevertheless, I has a MeOH ligand molecule, while for II-IV a DMF ligand replaces that of MeOH. The nature of the coordinated solvent molecule plays an important role in the behavior of the thermal dependence of the Y/B (yellow/blue) emission ratio of the DyIII complexes (Y: 4F9/2 → 6H13/2, yellow and B: 4F9/2 → 6H15/2, blue transitions),, since for I the variation of this ratio is significant, while for the other DyIII complexes with DMF as ligand the ratio remains constant within experimental error. At room temperature the CIE (Commission International d'Eclairage) color coordinates for the DyIII complexes, I (0.286, 0.317), III (0.302, 0.324), and IV (0.322, 0.348) are close to the NTSC (National Television System(s) Committee) standard value for white color. Varying the temperature from 16 to 300 K the CIE coordinates for I change from the blueish to white region of the chromaticity diagram, while those of II present an inverse thermal dependence as compared to I. The CCT (Correlated Color Temperature) values at room temperature for I (8384 K), II (17235 K), and IV (5948 K) permit us to consider these complexes as candidates for white cold light emitters, the high value of II being uncommon. For I and II the CCT values vary strongly with temperature, showing a decrease with increasing temperature for I, and an increase with increasing temperature for II, thus making evident the influence on the photophysical properties of the nature of the coordinated solvent molecule in these complexes.

Structural and Electronic Rearrangements in Fe2S2, Fe3S4, and Fe4S4 Atomic Clusters under the Attack of NO, CO, and O2.

We report results, based on density functional theory-generalized gradient approximation calculations, that shed light on how NO, CO, and O2 interact with Fe2S2, Fe3S4, and Fe4S4 clusters and how they modify their structural and electronic properties. The interest in these small iron sulfide clusters comes from the fact that they are at the protein cores and that elucidating fundamental aspects of their interaction with those light molecules which are known to modify their functionality may help in understanding complex behaviors in biological systems. CO and NO are found to bind molecularly, leading to moderate relaxations in the clusters, but nevertheless to changes in the spin-polarized electronic structure and related properties. In contrast, dissociative chemisorption of O2 is much more stable than molecular adsorption, giving rise to significant structural distortions, particularly in Fe4S4 that splits into two Fe2S2 subclusters. As a consequence, oxygen tends to strongly reduce the spin polarization in Fe and to weaken the Fe-Fe interaction inducing antiparallel couplings that, in the case of Fe4S4, clearly arise from indirect Fe-Fe exchange coupling mediated by O. The three molecules (particularly CO) enhance the stability of the iron-sulfur clusters. This increase is noticeably more pronounced for Fe2S2 than for the other iron-sulfur clusters of different compositions, a result that correlates with the fact that in recent experiments of CO reaction with FemSm (m = 1-4), the Fe2S2CO product results as a prominent one.

Comparative transcriptome analysis provides key insights into gene expression pattern during the formation of nodule-like structures in Brachypodium.

Auxins can induce the formation of nodule-like structures (NLS) in plant roots even in the absence of rhizobia and nitrogen-fixing bacteria can colonize these structures. Interestingly, NLS can be induced in roots of both legumes and non-legumes. However, our understanding of NLS formation in non-legumes at a molecular level is limited. This study aims to investigate NLS formation at a developmental and molecular level in Brachypodium distachyon. We treated Brachypodium roots with the synthetic auxin, 2,4-D, to induce NLS at a high frequency (> 80%) under controlled conditions. A broad base and a diffuse meristem characterized these structures. Next, we performed a comprehensive RNA-sequencing experiment to identify differentially expressed genes (DEGs) in Brachypodium roots during NLS formation. We identified 618 DEGs; several of which are promising candidates for control of NLS based on their biological and molecular functions. We validated the expression pattern of several genes via RT-PCR. Next, we compared the expression profile of Brachypodium roots with rice roots during NLS formation. We identified 76 single-copy ortholog pairs in rice and Brachypodium that are both differentially expressed during this process. Some of these genes are involved in auxin signaling, root development, and legume-rhizobia symbiosis. We established an experimental system to study NLS formation in Brachypodium at a developmental and genetic level, and used RNA-sequencing analysis to understand the molecular mechanisms controlling this root organogenesis program. Furthermore, our comparative transcriptome analysis in Brachypodium and rice identified a key set of genes for further investigating this genetic pathway in grasses.

Properties Design: Prediction and Experimental Validation of the Luminescence Properties of a New EuII -Based Phosphor.

A theoretical model that allows to predict, for the first time, the luminescence properties of a new phosphor (BaSnSi3 O9 :Eu2+ ) is presented. The predicted emission wavelength, 488 nm with a 64 nm bandwidth, was confirmed by subsequent experimental work. The method consists in a multi-electron Hamiltonian parametrized from ab initio calculations. The luminescence properties of other similar compounds (i.e., BaHfSi3 O9 :Eu2+ and BaZrSi3 O9 :Eu2+ ), for which there is already experimental information, were also correctly reproduced.

Predicting photon cascade emission in Pr3+ doped fluorides.

We present a theoretical approach, based on a density functional theoretic parametrization of a model Hamiltonian, that allows for the determination of the complete electronic 4fn and 4fn-15d valence manifolds of a lanthanide ion impurity in different host lattices in an easy, fast and reliable way. The model accounts for the electrostatic interactions, ligand field splitting due to the surroundings of the impurity and spin-orbit coupling effects, which means that the parametrization is transferable to different ligand environments. The model is applied to several Pr3+ doped fluorides, which are of great interest for designing warm white lighting devices. We show that the model correctly predicts which of them presents photon-cascade emission as experimentally observed. We also determine the absorption (emission) spectra from the dipolar transition probabilities from the lowest 4f2 (4f5d) state to the states of the 4f5d (4f2) manifold of the Pr3+ impurity, in agreement with the available experimental data. The present approach can be applied to other impurity-doped systems where the accurate determination of the valence impurity states is crucial for characterizing the relevant properties of the system.

1D magnetic interactions in Cu(II) oxovanadium phosphates (VPO), magnetic susceptibility, DFT, and single-crystal EPR.

We report the crystal face indexing and molecular spatial orientation, magnetic properties, electron paramagnetic resonance (EPR) spectra, and density functional theory (DFT) calculations of two previously reported oxovanadium phosphates functionalized with Cu(II) complexes, namely, [Cu(bipy)(VO2)(PO4)]n (1) and [{Cu(phen)}2(VO2(H2O)2)(H2PO4)2 (PO4)]n (2), where bipy = 2,2'-bipyridine and phen = 1,10-phenanthroline, obtained by a new synthetic route allowing the growth of single crystals appropriate for the EPR measurements. Compounds 1 and 2 crystallize in the triclinic group P1̅ and in the orthorhombic Pccn group, respectively, containing dinuclear copper units connected by two -O-P-O- bridges in 1 and by a single -O-P-O- bridge in 2, further connected through -O-P-O-V-O- bridges. We emphasize in our work the structural aspects related to the chemical paths that determine the magnetic properties. Magnetic susceptibility data indicate bulk antiferromagnetism for both compounds, allowing to calculate J = -43.0 cm(-1) (dCu-Cu = 5.07 Å; J defined as Hex(i,j) = -J Si·Sj), considering dinuclear units for 1, and J = -1.44 cm(-1) (dCu-Cu = 3.47 Å) using the molecular field approximation for 2. The single-crystal EPR study allows evaluation of the g matrices, which provide a better understanding of the electronic structure. The absence of structure of the EPR spectra arising from the dinuclear character of the compounds allows estimation of weak additional exchange couplings |J'| > 0.3 cm(-1) for 1 (dCu-Cu = 5.54 Å) and a smaller value of |J'| ≥ 0.15 cm(-1) for 2 (dCu-Cu = 6.59 Å). DFT calculations allow evaluating two different exchange couplings for each compound, specifically, J = -36.60 cm(-1) (dCu-Cu = 5.07 Å) and J' = 0.20 cm(-1) (dCu-Cu =5.54 Å) for 1 and J = -1.10 cm(-1) (dCu-Cu =3.47 Å) and J' = 0.01 cm(-1) (dCu-Cu = 6.59 Å) for 2, this last value being in the range of the uncertainties of the calculations. Thus, these values are in good agreement with those provided by magnetic and single-crystal EPR measurements.

A new magnetic superatom: Cr@Zn17.

We demonstrate, by means of fully unconstrained density functional theory calculations, that cluster Zn17 endohedrally doped with a Cr impurity can be qualified as a magnetic superalkali cluster. We explain the origin of its high stability, its low vertical ionization potential and its high total spin magnetic moment which amounts to 6 µB, exactly the same value as that of the isolated Cr atom. With the aim of exploring the possibility of designing a bistable magnetic nanoparticle, with a corresponding inter-unit exchange coupling, we also consider the assembling of two such units through different contact regions and in different magnetic configurations. Furthermore, we analyze up to which extent is the Zn shell able to preserve the electronic properties of the embedded Cr atom, both against coalescence of the two superatoms forming the magnetically bistable nanoparticle, and upon the adsorption of an O2 molecule or even under an oversaturated O2 atmosphere. Our results are discussed not only emphasizing the fundamental physical and chemical aspects, but also with an eye on the new prospects that those Cr@Zn17 magnetic superalkali clusters (and others of similar kind) may open in spintronics-, molecular electronics- or biomedical-applications.

Dual Emission of a Novel (P,N) Re(I) Complex: A Computational and Experimental Study on [P,N-{(C6H5)2(C5H4N)P}Re(CO)3Br].

The spectroscopic, electrochemical, and photophysical properties of the new complex [P,N-{(C6H5)2(C5H4N)P}Re(CO)3Br] are reported. The UV-vis spectrum in dichloromethane shows an absorption maximum centered at 315 nm and a shoulder at 350 nm. These absorption bands have been characterized to have MLCT character. Excitation at both wavelengths (maximum and shoulder) leads to an emission band centered at 550 nm. Cyclic voltammetry experiments show two ill-defined irreversible oxidation waves around +1.50 and 1.80 V that are assigned to Re(I)/Re(II) and Re(II)/Re(III) couples whereas an irreversible reduction signal centered at -1.80 V is likewise assigned to a ligand reduction process. These results support the proposal of the MLCT nature of the states implied by the emission of the complex. The luminescent decay fits to a biexponential function, where the lifetimes and emission quantum yields are dependent on the solvent polarity. DFT calculations suggest that dπ → π*pyridine and dπ → π*phenyl excited states may account for the existence of two decay lifetimes.