Physicochemical properties of ultrasmall colloidal silver nanoparticles: an experimental and computational approach.

Silver nanoparticles (AgNPs) exhibit very interesting properties that have been employed in several kinds of applications spanning from antibacterial activity to plasmon-polaritons generation. Nanoparticle size strongly influences these applications. However, the characterization of ultrasmall AgNPs (particle diameter < 10 nm) encompassing different aspects such as average size, polydispersion, shape (anisotropy), concentration, and density remains a challenging task. To address these challenges, we combined TEM measurements with a computational framework based on Mie-Gans theory. This allowed us to describe the aforementioned AgNP features accurately. The synthesis of AgNPs in an aqueous medium involved the use of silver nitrate as a chemical precursor and sodium borohydride as a reducing agent, with polyvinylpyrrolidone acting as a stabilizing agent. Our outcomes showed that increasing the concentration of the precursor and reducing agent with a fixed 1 : 2 molar ratio tends to yield ultrasmall AgNPs with low to moderate polydispersion, a nearly spherical shape (low anisotropy), concentration in the nanomolar range and density close to silver bulk. Also, we established an analytical expression that correlates the extinction molar absorptivity to AgNP size considering the nanoparticle shape. Notably, the computational framework proved to be highly effective in extracting crucial information about the AgNPs from UV-vis spectroscopy data. In conclusion, our study sheds light on the unique properties of ultrasmall AgNPs and presents a comprehensive approach for properly characterizing these nanoparticles, paving the way for further advancements in their applications.

Observation of the two-photon transition enhanced first hyperpolarizability spectra in cinnamaldehyde derivatives: A femtosecond regime study.

The application of nonlinear optical effects in optoelectronic devices is still scarce because the irradiance threshold necessary to induce a specific effect is very high. In this context, knowing the frequency-resolved first order molecular hyperpolarizability (ß) is essential to identifying regions where this response is intense enough to allow for applications in commercial devices. Thus, herein, we have determined the ß spectral dependence of five new push-pull cinnamylidene acetophenone derivatives using femtosecond laser-induced Hyper-Rayleigh Scattering (HRS). A considerable increase in ß values was observed in molecules. We found remarkable ß values in regions near the two-photon resonance, which are mediated by electron withdrawing and donating groups. This effect was mapped using wavelength-tunable femtosecond Z-scan technique. Furthermore, it was modeled in light of the sum-over-states approach for the second- and third-order nonlinearities. Finally, our outcomes suggest a strategy to obtain large ß values mediated by the 2PA transition.

Frequency-resolved microscopic second-order hyperpolarizability of azochromophores: a study on nonlinear all-optical switching applications.

Azochromophores present interesting optical properties for application in all-optical switches (AOSs), such as ultrafast photoisomerization and considerable nonlinear optical response. However, determining the frequency-resolved microscopic second-order hyperpolarizability (real and imaginary parts) related to the pure electronic effects of molecules in solution is a challenging task. In this context, we have used femtosecond-laser induced nonlinear ellipse rotation (NER) measurements to obtain the electronic nonlinear refraction (n2(ω)) and two-photon absorption spectra (α2PA(ω)) of four azochromophores dissolved in methanol and acetone. The measurements ranging from ∼600 up to ∼1300 nm were performed in Disperse Red 1 (DR1), Disperse Red 13 (DR13), Disperse Red 19 (DR19), and Disperse Orange 3 (DO3). Because we carried the solution in a silica cuvette and used a short focal length, we were able to measure the solution's nonlinearities with high precision, as the silica from the cuvette walls worked as a suitable reference medium. Consequently, we precisely determined n2(ω), α2PA(ω), and the second-order hyperpolarizability (γ(ω)) for all molecules and explained the different magnitudes based on the push-pull character. Furthermore, the solvation effect due to the change from methanol to acetone solvent on the n2(ω), α2PA(ω), and γ(ω) is also reported. The results were elucidated using the sum-over-states (SOS) approach within the few-energy-level model and the results were obtained via quantum-chemical calculations using the cubic response function formalism within the density functional theory framework. Finally, we used these results to determine the frequency-resolved figure-of-merit for all-optical switching applications. Our results suggest that chromophores have the potential for applications in AOS based on Fabry-Perot filters.

Unveiling the molecular structure and two-photon absorption properties relationship of branched oligofluorenes.

Organic molecules have been intensively studied during the last few decades because of their photonics and biological applications. In this material class, the fluorene molecules present outstanding optical features, for example, high values of two-photon absorption (2PA) cross-sections, visible transparency, and high fluorescence quantum yield. Also, it is possible to improve the nonlinear optical response by modifying the fluorene molecular structure. In this context, herein, we have synthesized V and Y-shaped branching oligofluorenes containing two and three fluorene moieties in each branch. Such a molecular strategy may exponentially enhance the nonlinear optical response due to the coherent coupling among the molecular arms. Thus, we combined the use of femtosecond Z-scan spectroscopy and white light transient absorption spectroscopy (TAS) to understand the molecular structure and 2PA property relationship of branching oligofluorenes. The results show that there is a universal relationship between the 2PA cross-section and the effective π-electron number (Neff) given by σ2PA(GM) = (079 ± 0.03)Neff2, which is independent of the molecular shape (linear, V or Y-shaped). Therefore, the intramolecular charge transfer responsible for the cooperative effect among the branches does not occur. This statement is corroborated by the results of the femtosecond TAS technique.

Size-dependent photoinduced transparency in colloidal CdTe quantum dots in the strong confinement regime: an inverse linear relationship.

Nanomaterials have been investigated as saturable absorbers for ultrafast lasers because of their large photoinduced transparency related to ground-state bleaching. However, the quantum dot size effect on the photoinduced transparency in the strong confinement regime has not been explored due to the challenge of accurately measuring the ground state and the excited-state absorption cross-sections. At the same time, these optical properties are essential to calculate several chemical and physical quantities at the nanoscale. In this context, we have employed the photoluminescence saturation method to determine the ground-state absorption cross-section and the femtosecond open-aperture Z-scan technique to investigate the size-dependent ground-state bleaching of glutathione-capped CdTe QDs synthesized in an aqueous medium. The results were modeled using rate equations within the three-energy levels approach. Our results pointed out that the photoinduced transparency rate at the 1S3/2(h) → 1S(e) transition peak presents an inverse linear relationship with the QD diameter (from 2.2 nm up to 3 nm). Otherwise, the larger QDs have a higher ground-state cross-section, which is directly proportional to the ground-state bleaching. To explain this apparent contradiction, we calculate the effective absorption coefficient αeff = σ/V (σ is the absorption cross section and V is the QD volume) for the QDs and observed that the smaller QDs have a higher absorption from the ground to the first excited state, corroborating our results. Finally, our results showed that the saturable absorption effect in CdTe-QDs is slightly higher than that obtained for graphene and other 2D materials and smaller than the black phosphorus in the visible region.

Size-Dependent Photobleaching Mechanism and Kinetics Induced by Nanosecond Laser Pulses in Colloidal Semiconductor Quantum Dots.

An experimental-theoretical approach is proposed to investigate the size-dependent photobleaching of colloidal semiconductor quantum dots (QDs) excited by a nanosecond pulsed laser. In the experimental background, the ground-state absorption and photoluminescence (PL) spectra of chemically prepared QDs are monitored over an excitation time at distinct laser irradiances. The magnitude of photobleaching in the QD solution is quantified by the decay rate of the PL signal as a function of the excitation time and the laser power. A theoretical spectroscopy model is then used to estimate the particle size distribution (PSD) in colloidal solution from the absorption data generated at different laser powers. The resulting evolution of the PSD of the QD ensemble under irradiation is analyzed in terms of classical crystallization theories dealing with the formation, growth, and dissolution of colloidal particles in a supersaturated medium. The QD response to laser irradiation is also interpreted by a simple mechanical model that correlates the photoinduced hydrostatic strain at the solid/liquid interface and the predicted variation of the mean particle size. The reported experimental and theoretical methods are used to completely elucidate the basic physico-chemical processes responsible for the laser-induced photobleaching kinetics of glutathione-capped CdTe aqueous QDs with very small mean sizes. For this purpose, we synthesized a series of colloidal QD samples with mean particle diameters ranging from 1.95 to 2.68 nm. Our results indicate that a faster photobleaching rate occurs in QD samples with smaller sizes in which particle dissolution under laser irradiation is predominant. On the other hand, the photobleaching rate becomes slower in samples with larger dot sizes, possibly due to the formation of core/shell structures in solution via thermal degradation of thiol ligands either during the chemical synthesis or as a consequence of the subsequent interaction with the excitation laser.

Effective π-electron number and symmetry perturbation effect on the two-photon absorption of oligofluorenes.

Fluorene-based molecules exhibit significant nonlinear optical responses and multiphoton absorption in the visible region, which, combined with the high fluorescence quantum yield in organic solvents, could make this class of materials potentially engaging in diverse photonics applications. Thus, herein, we have determined the two-photon absorption (2PA) of oligofluorenes containing three, five, and seven repetitive units by employing the wavelength-tunable femtosecond Z-scan technique. Our outcomes have shown that the 2PA cross-section in oligofluorenes presents an enhanced value of around 18 GM per Neff, in which Neff is the effective number of π-electrons, for the pure 2PA allowed transition (11Ag-like → 21Ag-like). Furthermore, a weak 2PA transition was observed in the same spectral region strongly allowed by one-photon absorption (11Ag-like → 11Bu-like). This last result suggests a molecular symmetry perturbation, probably induced by the molecular disorder triggered by the increase of moieties in the oligofluorene structure. We have calculated the permanent dipole moment difference related to the lowest-energy transition using the Lippert-Matagaformalism and the 2PA sum-over-states approach to confirm this assumption. Moreover, we have estimated the fundamental limits for the 2PA cross-section in oligofluorenes.

Photobleaching Kinetics of MEH-PPV in Solution: The Role of Conformational Disorder.

Semiconductor polymers are the foundation of organic electronics due to their remarkable optical features, ability to form a thin film, and low cost compared to silicon. However, some of them have intense photobleaching under UV-blue radiation, compromising several applications. In this context, we have investigated the conformational disorder effect on the real-time photobleaching kinetics of a poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV)/chloroform solution under deep-blue radiation. Our results pointed out that a 405 nm diode laser initially causes a significant conformational disorder in the π-conjugated backbone of MEH-PPV as revealed by the Huang-Rhys factor. As a result, a new vibrational mode arises with an energy separation of 230 meV, indicating the substitution of the vinyl (C═C) by carbonyl (C═O) bonds. Then, the conformational disorder reaches a maximum value at some tens of minutes, which is inversely proportional to the polymer concentration, and after that, a random chain scission occurs. Consequently, the effective conjugation length of MEH-PPV in chloroform decreases from nine to three coplanar repetitive units after 1 h of excitation, producing a drastic drop in photoluminescence. Finally, we show that the photobleaching steps are mapped through the conformational disorder.

Molecular Structure-Optical Property Relationship of Salicylidene Derivatives: A Study on the First-Order Hyperpolarizability.

The first-order hyperpolarizability of π-conjugated organic molecules is of particular interest for the fabrication of electro-optical modulators. Thus, we investigated the relationship between the molecular structure and the incoherent second-order nonlinear optical response (ßHRS) of four salicylidene derivatives (salophen, [Zn(salophen)(OH2)], 3,4-benzophen, [Zn(3,4-benzophen)(OH2)]) dissolved in DMSO. For that, we employed the Hyper-Rayleigh Scattering technique with picosecond pulse trains. Our experimental results pointed out dynamic ßHRS values between 32.0 ± 4.8 × 10-30 cm5/esu and 58.5 ± 8.0 × 10-30 cm5/esu at 1064 nm, depending on the molecular geometry of the salicylidene molecules. More specifically, the outcomes indicate a considerable increase of ßHRS magnitude (∼30%) when in the ligands are incorporated the Zn(II) ion. We ascribed such results to the rise of the planarity of the π-conjugated backbone of the chromophores caused by the Zn(II). Furthermore, we observed an increase of ∼50% in dynamic ßHRS when there is a replacement of one hydrogen atom (salophen molecule) by an acetophenone group (3,4-benzophen). This result is related to the increase of the effective π-electron number and the higher charge transfer induced at the excited state. All these findings were interpreted and supported in the light of time-dependent density functional theory (DFT) calculations. Solvent effects were considered in the quantum chemical calculations using the integral equation formalism variant of the polarizable continuum model.

Combined selection for adaptability, genotypic stability and cowpea yield from mixed models / Seleção combinada para adaptabilidade, estabilidade genotípica e produtividade de feijão-caupi a partir de modelos mistos

ABSTRACT: The potential expression of crop productivity is a constant challenge for plant breeders in the face of oscillations in environmental variables, making selection difficult and increasing the operational and methodological costs in obtaining the ideal cultivar for a determined region. The objective of the research was to investigate the effects of genotype x environment interaction in the selection of cowpea lines with high grain yield, adaptability, and genotypic stability simultaneously, in environments of the Northwest region of Rio de Janeiro State, using mixed models (Maximum Restricted Likelihood - REML/Best Linear Unbiased Prediction - BLUP). 27 cowpea genotypes were evaluated in six environments by combining location (Cambuci-RJ and Bom Jesus do Itabapoana-RJ) and year (2016, 2017 and 2018). A randomized block design with four replications was performed. The genetic parameters were estimated via the REML/BLUP procedure, and the selection was based on the harmonic mean method of the relative performance of the genetic values (HMRPGV). A meaningful difference was observed for environment and genotype x environment interaction. The residual variance and the variance of the genotype x environment interaction formed the most significant fractions of the phenotypic variance. Lines 4 (Bico-de-ouro 1-5-24), 6 (Pingo-de-Ouro 1-5-4), 5 (Pingo-de-Ouro 1-5-26), and 9 (Pingo-de-Ouro 1-5-8), stood out as superior in terms of stability and adaptability and grain yield by HMRPGV. Commercial cultivars 13 (BRS-Tumucumaque) and 26 (BRS-Itaim) had high grain yield, adaptability, and specific stability in the evaluated edaphoclimatic conditions.

RESUMO: A expressão potencial da produtividade das culturas constitui um desafio constante aos criadores de plantas frente às oscilações das variáveis ambientais, dificultando a seleção e onerando os custos operacionais e metodológicos na obtenção da cultivar ideal para determinada região. O objetivo do trabalho foi investigar os efeitos da interação genótipos x ambientes na seleção de linhagens de feijão-caupi com alta produtividade de grãos, adaptabilidade e estabilidade genotípica simultaneamente, em ambientes da região Noroeste do estado do Rio de Janeiro, usando modelos mistos (Máximo Verosimilhança Restrita - REML/Melhor Predição Linear não Viesado - BLUP). Avaliou-se 27 genótipos de feijão-caupi em seis ambientes pela combinação de local (Cambuci-RJ e Bom Jesus do Itabapoana-RJ) e ano (2016, 2017 e 2018). Foi utilizado o delineamento em blocos casualizados com quatro repetições. Os parâmetros genéticos foram estimados via procedimento REML/BLUP, e a seleção baseou-se no método da média harmônica do desempenho relativo dos valores genéticos (HMRPGV). Observou-se diferença significativa para ambiente e interação genótipo x ambiente. A variância residual e a variância da interação genótipo x ambiente formaram as maiores frações da variância fenotípica. As linhagens 4 (Bico-de-ouro 1-5-24), 6 (Pingo-de-ouro 1-5-4), 5 (Pingo-de-ouro 1-5-26) e 9 (Pingo-de-ouro 1-5-8) foram classificadas como superiores quanto a estabilidade e adaptabilidade e rendimento de grãos pelo critério da HMRPGV. As cultivares comerciais 13 (BRS-Tumucumaque) e 26 (BRS-Itaim) reuniram elevada produtividade de grãos, adaptabilidade e estabilidade específica nas condições edafoclimáticas avaliadas.

Comparison of Selection Traits for Effective Popcorn (Zea mays L. var. Everta) Breeding Under Water Limiting Conditions.

Climate change is expected to intensify water restriction to crops, impacting on the yield potential of crops such as popcorn. This work aimed to evaluate the performance of 10 field cultivated popcorn inbred lines during two growing seasons, under well-watered (WW) and water stressed (WS) (ψsoil≥ -1.5 MPa) conditions. Water stress was applied by withholding irrigation in the phenological phase of male pre-anthesis. Additionally, two contrasting inbred lines, P7 (superior line) and L75 (low performer) were compared for grain yield (GY) and expanded popcorn volume (EPV), selected from previous studies, were tested under greenhouse conditions. In the field, no genotype x water condition x crop season (G×WC×CS) interaction was observed, whereas GY (-51%), EPV (-55%) and leaf greenness (SPAD index) measured 17 days after anthesis (DAA) (> -10%) were highly affected by water limitation. In general, root traits (angles, number, and density) presented G×WC×CS interaction, which did not support their use as selection parameters. In relation to leaf senescence, for both WS and WW conditions, the superior inbred lines maintained a stay-green condition (higher SPAD index) until physiological maturity, but maximum SPAD index values were observed later in WW (48.7 by 14 DAA) than in WS (43.9 by 7 DAA). Under both water conditions, negative associations were observed between SPAD index values 15 and 8 days before anthesis DBA), and GY and EPV (r ≥ -0.69), as well as between SPAD index 7, 17, and 22 DAA, and angles of brace root (AB), number of crown roots (NC) and crown root density (CD), in WS (r ≥ -0.69), and AB and CD, in WW (r ≥ -0.70). Lower NC and CD values may allow further root deepening in WS conditions. Under WS P7 maintained higher net photosynthesis values, stomatal conductance, and transpiration, than L75. Additionally, L75 exhibited a lower (i.e., more negative) carbon isotope composition value than P7 under WS, confirming a lower stomatal aperture in L75. In summary, besides leaf greenness, traits related to leaf photosynthetic status, and stomatal conductance were shown to be good indicators of the agronomic performance of popcorn under water constraint.

Probing the Strong Near-IR Two-Photon Transition in Supramolecular Triphenylamine-based Polymers by Nonlinear Absorption Spectroscopy.

Due to their capability of film formation and remarkable optical features, semiconductor polymers with high two-photon absorption (2PA) have been studied as potential candidates for the development of organic photonic platforms. Furthermore, there is a high demand for photonic devices operating in the near-infrared (IR) region. However, the magnitude of the nonlinear optical response of random coil polymers in the IR region is weak due to the loss of molecular structure caused by increasing the π-conjugated backbone. Thus, herein we aim to investigate the molecular structure and 2PA features relationship for four polymers with supramolecular (helical) rodlike structure. Such polymers have a rigid core based on triphenylamine groups connected to the chiral binaphthalene units and a strong electron-withdrawing group (EWG). This kind of structure allows a very high chromophore density, which was responsible for generating 2PA cross-section between 305 GM and 565 GM in the near-IR (900-1300 nm), depending on the EWG strength. in light of the two-level model within the sum-overstates approach, we estimated the degree of intramolecular charge transfer induced by 2PA in the IR region, and values as high as 50-70% were found. Such a critical outcome allows the 2PA cross-section in the IR region to remain high even though the ratio between the visible/IR-band 2PA cross-section increases as a function of EWG strength.

Repeatability estimates and minimum number of evaluations for selection of elephant-grass genotypes for herbage production / Estimativas de repetibilidade e número mínimo de avaliações para seleção de genótipos de capim-elefante para produção de forragem

In forage-plants breeding, the selection of superior genotypes has been undertaken through successive harvests in previously established intervals. However, this process involves many steps, the evaluation of many traits, and a great spending with costs and labor. Thus the estimate of the repeatability is essential in improvement of perennials, it allows predicting genotypic value of the individual, the minimum number of evaluations in the selection of genotypes and minimizes resources and time in the selection of promising individuals. The objective of this study was to estimate the repeatability coefficient for morphological traits in elephant grass and determine the number of evaluations needed for phenotypic selection more efficient. The experimental randomized block design with 53 genotypes and two replications. The repeatability coefficients were estimated for variables plant height, number of tillers, stem diameter and dry matter yield, using the methods of Anova, Principal Components and Structural Analysis. We observed significant differences between genotypes (P <0.01) for all variables. The main components provide larger estimates of repeatability when compared to other methods. Estimates of the repeatability coefficients are of high magnitude average for the variables plant height (0.44) number of tillers (0.44) and stem diameter (0.63) and low magnitude for dry matter production (0.27). The Principal Components method requires five, five, two and eleven measurements for plant height, number of tillers, stem diameter and dry matter yield, respectively, with 80% reliability.

No melhoramento de plantas forrageiras, a seleção de genótipos superiores tem sido realizada mediante a realização de cortes sucessivos em intervalos previamente estabelecidos. Entretanto este processo envolve muitas etapas, avaliação de muitos caracteres e um grande dispêndio de custos e mão-de-obra. Assim, a estimativa da repetibilidade é essencial no melhoramento de plantas perenes, pois permite predizer o valor genotípico do indivíduo, o número mínimo de avaliações na seleção de genótipos e minimiza recursos e tempo na seleção de indivíduos promissores. O objetivo deste trabalho foi obter estimativas do coeficiente de repetibilidade para caracteres morfoagronômicos em capim-elefante e determinar o número de avaliações necessárias para seleção fenotípica com maior eficiência. Utilizou-se delineamento experimental de blocos casualizados com 53 genótipos e duas repetições. Foram estimados os coeficientes de repetibilidade para as variáveis altura de plantas (ALT), número de perfilhos (NP), diâmetro de colmo (DC) e produtividade de matéria seca (PMS), utilizando-se os métodos da Anova, Componentes principais e Análise estrutural. Observaram-se diferenças significativas entre os genótipos (p<0,01) para todas as variáveis avaliadas. Os componentes principais proporcionam maiores estimativas de repetibilidade em relação aos demais métodos. As estimativas dos coeficientes de repetibilidade são de média a alta magnitude, para as variáveis ALT, NP e DC e de baixa magnitude para PMS. Com base no método dos Componentes Principais são necessárias cinco, cinco, duas e onze medidas para altura da planta, número de perfilhos, diâmetro do caule e rendimento de matéria seca, respectivamente, com 80% de confiabilidade.

Probing the high performance of photoinduced birefringence in V-shaped azo/PMMA guest-host films.

Optical birefringence in polymeric films containing azo-chromophores is an important feature related to the development of several technologies such as electro-optic modulators, optical switching, and optical gates, to cite a few. Therefore, it is essential to understand the main underlying mechanisms describing dynamic switching. In this context, we have investigated the optical birefringence performance of a guest-host film produced from a poly(methyl methacrylate) (PMMA) matrix containing a V-shaped azo-chromophore, which exhibited a larger optical response in comparison to the linear chromophores. The optical birefringence was induced by a linearly polarized diode laser (532 nm, writing laser), while a low-intensity HeNe (632.8 nm) laser and a tungsten-halogen lamp are employed, respectively, to monitor the optical storage and the absorption change during the photoinduced birefringence. Our results pointed out that the guest-host film presents maximum residual optical memory at around 50% and local optical birefringence at around 3.3 × 10-4 in the low concentration and intensity regimes. The high optical birefringence obtained in guest-host films was attributed to the considerable photoisomerization quantum yield in the solid-state (0.15 ± 0.02 for 532 nm). Besides, we have shown that the switching mechanism is driven by angular hole-burning during the first seconds after excitation, and, subsequently, molecular reorientation quickly rises, dominating the photochemical process. The latter mechanism is highly efficient in converting cis to trans molecules (100%), which is responsible for the high residual optical memory obtained. In order to better understand the isomerization mechanism of the azo-chromophore/PMMA film, we performed quantum chemical calculations within the DFT framework. The electronic transitions of the azo-chromophore isomers were determined using the TD-DFT method and potential energy curves (PECs) were constructed to investigate the possibility of the thermal-isomerization process of the V-shaped azo-chromophore through both rotation and inversion mechanisms. For both mechanisms, the amplitude of the energy barrier and activation energy for thermal isomerization are determined and the results are discussed.

SNP-based mixed model association of growth- and yield-related traits in popcorn.

The identification of the genes responsible for complex traits is highly promising to accelerate crop breeding, but such information is still limited for popcorn. Thus, in the present study, a mixed linear model-based association analysis (MLMA) was applied for six important popcorn traits: plant and ear height, 100-grain weight, popping expansion, grain yield and expanded popcorn volume per hectare. To this end, 196 plants of the open-pollinated popcorn population UENF-14 were sampled, selfed (S1), and then genotyped with a panel of 10,507 single nucleotide polymorphisms (SNPs) markers distributed throughout the genome. The six traits were studied under two environments [Campos dos Goytacazes-RJ (ENV1) and Itaocara-RJ (ENV2)] in an incomplete block design. Based on the phenotypic data of the S1 progenies and on the genetic characteristics of the parents, the MLMA was performed. Thereafter, genes annotated in the MaizeGDB platform were screened for potential linkage disequilibrium with the SNPs associated to the six evaluated traits. Overall, seven and eight genes were identified as associated with the traits in ENV1 and ENV2, respectively, and proteins encoded by these genes were evaluated for their function. The results obtained here contribute to increase knowledge on the genetic architecture of the six evaluated traits and might be used for marker-assisted selection in breeding programs.

Genetic effects on the efficiency and responsiveness to phosphorus use in popcorn as estimated by diallel analysis.

Agricultural expansion and the need for sustainable cultivation are challenges faced by researchers involved in the generation of new cultivars that can adapt to abiotic stress. Knowledge of the genetic effects of characteristics related to efficiency and responsiveness to phosphorus use must be considered when implementing methods to obtain better genotypes. The aim of this study was to characterize and select popcorn hybrids based on their efficiency and responsiveness to phosphorus use, and estimate their combining abilities and genetic effects via diallel analysis to implement improvement programs for sustainable agriculture. Eight contrasting inbred lines were used to obtain simple hybrids for diallel analysis. Twenty-eight diallelic hybrids plus the popcorn parental lines were evaluated at two different sites under two contrasting environments for soil phosphorus availability (6 × 6 lattice design). Grain yield, popping expansion, and volume of expanded popcorn per hectare were measured. A combined analysis of variance and a test of means were performed. The classification and utilization of the phosphorus use efficiency index, according to the grain yield performance of the hybrids under contrasting environments, was considered. Through model 2 of the Griffing's diallel analysis method, the general and specific combining abilities were estimated, along with their environmental interactions. The best strategy to obtain genotypes that are efficient and responsive to phosphorus involves exploring popcorn hybrids using genitors that result in the accumulation of additive genes that promote popping expansion. Hybrids P7 × L80, P7 × L59, P7 × L76, and P6 × L80 presented promising results and may be evaluated as cultivation options in phosphorus-deficient soils.

Intramolecular Cooperative and Anti-Cooperative Effect on the Two-Photon Absorption Cross Section in Triphenylamine Derivatives.

The intramolecular cooperative effect in branched molecules is a consequence of the interaction and extent of electronic coupling among the different axes of charge transfer. Such an effect is the key to obtain remarkable nonlinear optical response in molecular systems. Here we show that triphenylamine derivative molecules containing only two branches present the strongest electronic interaction between them at the excited state, generating exponential enhancement of the 2PA cross section. The primary factor for such behavior was ascribed to the substantial extent and interaction of the π-electron delocalization promoted by the strong electron-donating and acceptor antisymmetrical groups present in each branch. However, for the three-branch molecules we observed an anticooperative effect, i.e., the 2PA cross section decreases as compared to the one-branch structure as we normalized the signal by the effective π-electron number in each molecule.

Absolute Nonlinear Refractive Index Spectra Determination of Organic Molecules in Solutions.

It has been a great challenge to measure the spectrum of pure bound-electronic third-order nonlinear refraction ( n2) of organic chromophores in solutions because of the spurious contribution from the solvent and cuvette walls. In order to circumvent this problem, we present here a new method to obtain a highly accurate absolute n2 value of organic molecules in solutions with a self-referenced nonlinear ellipse rotation (NER) technique. As a proof of concept, we measured n2 spectra of two well-known chromophores, rhodamines B and 6G dissolved in methanol, in the range from ∼600 to 1200 nm. Our results pointed out that these two dyes present similar dispersion curves with strong negative nonlinearities near the one-photon absorption band and small positive values at long wavelengths. Furthermore, the negative signal of the dyes can be strong enough to cancel and even invert the positive nonlinear refraction of the solvent (methanol) as the solution's concentration increases. To understand the n2 spectrum and its connection to molecular properties of organic chromophores, we employed the sum-over-states (SOS) approach within the few-energy-level model and observed an excellent agreement between the experimental and theoretical spectra. In this way, we believe that, employing our NER technique and the SOS model, it is possible to determine both experimentally and theoretically the absolute magnitude and spectra of pure electronic n2 for a large variety of other organic molecules.

Estimation of genetic merit of diallel hybrids of sweet pepper by mixed models / Estimação do mérito genético de híbridos dialélicos de pimentão sob cultivo hidropônico via modelos mistos

ABSTRACT: The use of mixed models for evaluating diallel crosses is a highly timely option to the reliable prediction of progeny genetic values. In the sweet pepper crop, hybrids are commercially explored on a large scale, mainly because of their characteristics of economic importance. This study aimed to assess the potential of hybrids obtained from a partial diallel among five sweet pepper lines developed for the hydroponic cultivation system and two simple hybrids, by applying mixed models. It was performed crosses in the partial diallel scheme among the (L1B, L6, L7, L18, and L19) lines and the simple hybrids 'Valdor' and 'Atlantis'. Plants were cultivated in hydroponic system with substrate and irrigated three times a day using nutrient solution. On the basis of mixed models, the following traits were assessed: mean fruit diameter (FD), mean fruit length (FL), mean fruit number per plant (FNP), mean fruit mass (FM), early yield (EYIELD), and mean fruit mass per plant (FMP). The L6 line was the one that showed the highest estimate of general combination capacity for FMP, FM, and EYIELD, proving to be promising for recommendation. The hybrid that provided the best specific combining ability for FD, FM, FMP, and EYIELD was L6 x 'Valdor'. Triple hybrids were efficient to maximize yield for the traits of interest by the use of the mixed model.

RESUMO: A utilização de modelos mistos na avaliação de cruzamentos dialélicos é uma opção altamente oportuna para a fidedigna predição dos valores genéticos das progênies. Na cultura do pimentão, os híbridos são largamente explorados comercialmente, principalmente por suas características de importância econômica. O objetivo deste trabalho foi avaliar o potencial de híbridos resultantes de um dialelo parcial entre cinco linhagens de pimentão desenvolvidas para o sistema de cultivo hidropônico e dois híbridos simples, utilizando modelos mistos. Foram realizados cruzamentos no esquema de dialelo parcial entre as linhagens (L1B, L6, L7, L18 e L19) e os híbridos simples 'Valdor' e 'Atlantis'. As plantas foram cultivadas em sistema hidropônico com substrato e irrigadas três vezes ao dia com solução nutritiva. Com base em modelos mistos, foram avaliadas as características: diâmetro médio de frutos (DF); comprimento médio de frutos (CF); número médio de frutos por planta (NFP); massa média de frutos (MMF); produção precoce (PP) e massa média de frutos por planta (MFP). A linhagem L6 foi a que expressou maior estimativa de capacidade geral de combinação para MFP, MMF e PP, revelando-se promissora para recomendação. O híbrido triplo que apresentou melhor capacidade específica de combinação para DF, MMF, MFP e PP, foi L6 x 'Valdor'. Os híbridos triplos foram eficientes para incrementar a produtividade para as características de interesse com a aplicação da modelagem mista.

The GT biplot analysis of green bean traits / Análise GT biplot para características de feijão-vagem

ABSTRACT: The green bean (Phaseolus vulgaris L.) is a nutrient-rich vegetable much appreciated; although, little studied, in Brazil. The aim of the current study was to investigate the nature of traits of interest, as well as to select plants for the green bean breeding program based on genotype vs. trait biplot analysis. The experiment followed a randomized block design, with 4 repetitions and 17 genotypes. Analysis of variance, principal component analysis and biplot charts were performed to analyze the number of pods per plant, the number of seeds per pod, the number of seeds per plant, seed weight per plant, 100-seed weight, as well as grain and pod yields. The analysis of variance showed genetic variability between genotypes. Grain yield, pod yield and seed weight per plant were highly correlated. The number of seeds per pod was negatively correlated with pod weight, grain weight and with seed weight per plant. Lines Feltrin and UENF 14-30-3 were indicated to increase gains in variables such as grain yield and pod yield.

RESUMO: O feijão-vagem (Phaseolus vulgaris L.) é uma hortaliça rica em nutrientes, muito apreciada no Brasil, mas pouco estudada. O objetivo deste trabalho foi conhecer a natureza das características de interesse e selecionar plantas, para seguir o programa de melhoramento de feijão-vagem, por meio da análise biplot de genótipo x característica. O delineamento utilizado foi de blocos casualizados com quatro repetições e 17 genótipos. Foram feitas análise de variância, análise de componentes principais e os gráficos bilots para número de vagem por planta, número de sementes por vagem, número de sementes por planta, peso de sementes por planta, peso de 100 sementes, produtividade de grãos e produtividade de vagem. A análise de variância mostrou existência de variabilidade genética entre os genótipos. Produtividade de grãos, produtividade de vagens e peso de sementes por plantas são altamente correlacionados. O número de sementes por vagem tem correlação negativa com peso de vagem, peso de grãos e peso de sementes por planta. Os genótipos Feltrin e UENF 14-30-3 foram indicadas para obtenção de ganhos para as variáveis produtividade de grãos e produtividade de vagem.