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1.
J Chem Phys ; 156(14): 144305, 2022 Apr 14.
Artigo em Inglês | MEDLINE | ID: mdl-35428387

RESUMO

Recurrent fluorescence (RF) from isolated carbon clusters containing between 24 and 60 atoms is theoretically investigated as a function of internal energy, cluster size, and structural features. The vibrational relaxation kinetics and the associated IR emission spectra are determined by means of a Monte Carlo approach with vibrational density of states computed in the harmonic approximation. RF is generally found to be highly competitive with vibrational emission. The behaviors predicted for clusters of various sizes and archetypal structures indicate that the IR emission spectra are strongly influenced by RF, an energy gap law being obtained for the evolution of the RF rate constant depending on the electronic excitation state. The present results are relevant to the photophysics of the interstellar medium and could contribute to elucidating the carriers of the extended red emission bands and the continuum emission lying below the aromatic infrared bands believed to originate from mixed aromatic-aliphatic compounds.

2.
Br J Surg ; 108(10): 1251-1258, 2021 10 23.
Artigo em Inglês | MEDLINE | ID: mdl-34240110

RESUMO

BACKGROUND: The purpose of this study was to investigate the prevalence of ypN+ status according to ypT category in patients with locally advanced rectal cancer treated with chemoradiotherapy and total mesorectal excision, and to assess the impact of ypN+ on disease recurrence and survival by pooled analysis of individual-patient data. METHODS: Individual-patient data from 10 studies of chemoradiotherapy for rectal cancer were included. Pooled rates of ypN+ disease were calculated with 95 per cent confidence interval for each ypT category. Kaplan-Meier and Cox regression analyses were undertaken to assess influence of ypN status on 5-year disease-free survival (DFS) and overall survival (OS). RESULTS: Data on 1898 patients were included in the study. Median follow-up was 50 (range 0-219) months. The pooled rate of ypN+ disease was 7 per cent for ypT0, 12 per cent for ypT1, 17 per cent for ypT2, 40 per cent for ypT3, and 46 per cent for ypT4 tumours. Patients with ypN+ disease had lower 5-year DFS and OS (46.2 and 63.4 per cent respectively) than patients with ypN0 tumours (74.5 and 83.2 per cent) (P < 0.001). Cox regression analyses showed ypN+ status to be an independent predictor of recurrence and death. CONCLUSION: Risk of nodal metastases (ypN+) after chemoradiotherapy increases with advancing ypT category and needs to be considered if an organ-preserving strategy is contemplated.


When patients are diagnosed with rectal cancer and the tumour grows beyond the rectal wall there is a high risk that the tumour has spread to nearby lymph nodes. This study showed that this relationship between tumour invasion depth and lymph node involvement is similar after treatment with (chemo)radiotherapy. Patients who have tumour cells remaining in the lymph nodes after (chemo) radiotherapy have a worse prognosis than patients who do not have cancer cells remaining in the lymph nodes. When an organ-preserving treatment is considered as an alternative therapy, this should be kept in mind during patient counselling.


Assuntos
Linfonodos/patologia , Metástase Linfática , Neoplasias Retais/patologia , Neoplasias Retais/terapia , Idoso , Idoso de 80 Anos ou mais , Quimiorradioterapia Adjuvante , Feminino , Humanos , Estimativa de Kaplan-Meier , Masculino , Pessoa de Meia-Idade , Invasividade Neoplásica , Recidiva Local de Neoplasia , Protectomia , Neoplasias Retais/cirurgia , Análise de Regressão
3.
Ann Oncol ; 31(7): 861-872, 2020 07.
Artigo em Inglês | MEDLINE | ID: mdl-32272210

RESUMO

A Japan Society of Clinical Oncology (JSCO)-hosted expert meeting was held in Japan on 27 October 2019, which comprised experts from the JSCO, the Japanese Society of Medical Oncology (JSMO), the European Society for Medical Oncology (ESMO), the American Society of Clinical Oncology (ASCO), and the Taiwan Oncology Society (TOS). The purpose of the meeting was to focus on what we have learnt from both microsatellite instability (MSI)/deficient mismatch repair (dMMR) biomarkers in predicting the efficacy of anti-programmed death-1 (PD-1)/programmed death ligand-1 (PD-L1) immunotherapy, and the neurotrophic tyrosine receptor kinase (NTRK) gene fusions in predicting the efficacy of inhibitors of the tropomyosin receptor kinase (TRK) proteins across a range of solid tumour types. The recent regulatory approvals of the anti-PD-1 antibody pembrolizumab and the TRK inhibitors larotrectinib and entrectinib, based on specific tumour biomarkers rather than specific tumour type, have heralded a paradigm shift in cancer treatment approaches. The purpose of the meeting was to develop international expert consensus recommendations on the use of such tumour-agnostic treatments in patients with solid tumours. The aim was to generate a reference document for clinical practice, for pharmaceutical companies in the design of clinical trials, for ethics committees in the approval of clinical trial protocols and for regulatory authorities in relation to drug approvals, with a particular emphasis on diagnostic testing and patient selection.


Assuntos
Ensaios Clínicos como Assunto , Instabilidade de Microssatélites , Neoplasias , Humanos , Consenso , Japão , Oncologia , Neoplasias/tratamento farmacológico , Neoplasias/genética , Taiwan
4.
Phys Chem Chem Phys ; 22(22): 12465-12475, 2020 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-32462154

RESUMO

The stepwise solvation of various cationic coronene oligomers by para-hydrogen (p-H2) molecules was computationally investigated using a united-atom model for the p-H2 molecules and the Silvera-Goldman potential, together with a polarizable description for the interaction with the hydrocarbon molecules. A survey of the energy landscape for oligomers containing between 1 and 4 coronene molecules and possible different conformers was carried out using standard global optimization, the hydrocarbon complex being kept as rigid. The most stable structures provided the starting configuration of systematic path-integral molecular dynamics simulations at 2 K. The variations of the geometric and energetic properties of the solvation shell were determined with increasing number of para-hydrogen molecules. The relative stability of the solvation shell is generally found to be more robustly determined by the energy increment (or dissociation energy) than by geometrical indicators, especially when the oligomers have less ordered structures. In agreement with recent mass spectrometry experiments, the size at which the first solvation shell is complete is found to vary approximately linearly with the oligomer size when the coronene molecules stack together, with a slope that is related to the offset between two successive molecules.

5.
Phys Chem Chem Phys ; 21(9): 5123-5132, 2019 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-30766988

RESUMO

The aggregation and physical growth of polycyclic aromatic hydrocarbon (PAH) molecules was simulated using a coarse-grained (CG) approach based on the Paramonov-Yaliraki (PY) potential and a stochastic Monte Carlo framework, following earlier efforts in which the structure [Phys. Chem. Chem. Phys., 2016, 18, 13736] and equilibrium thermodynamics [Phys. Chem. Chem. Phys., 2017, 19, 1884] were investigated and critically compared to the predictions of all-atom models. Homomolecular and heteromolecular assemblies of pyrene, coronene, and circumcoronene were considered at various temperatures and compositions, and the distributions of aggregation products were characterized. Under the simulated conditions, and in agreement with earlier studies, the clusters are rather small and, in the case of pyrene-rich systems, only formed below 1000 K. The clusters obtained by spontaneous aggregation of isolated molecules are statistically analysed. For the selected sizes of tetramers and octamers, broad distributions of isomers are obtained with a clear entropic stabilization. In heteronuclear assemblies, our results suggest a minor spontaneous segregation towards pure and equi concentrations at variance with purely statistical expectations.

6.
J Phys Chem A ; 123(1): 202-209, 2019 Jan 10.
Artigo em Inglês | MEDLINE | ID: mdl-30525626

RESUMO

The stable structures of odd-numbered anionic nitrogen clusters, N2 n+3-, have been theoretically investigated in the size range n = 1-9 using a variety of quantum chemistry methods that include perturbation theory, coupled cluster, and density-functional theory with different exchange-correlation functionals. We generally find that the clusters are composed of an azide chromophore N3- surrounded by essentially neutral nitrogen molecules. The growth initially proceeds by placing the neutral molecules parallel to the azide anion, completing a first shell at N13-, above which the extra molecules arrange on the side but with a significantly lower binding energy. Comparison with the cyclic N5- anionic core shows that the latter is unfavorable, the spectral signatures of both N5- and N2N3- being provided in both the infrared and ultraviolet ranges. The trend of these clusters to be highly stable as (N2) nN3- agrees with recent mass spectrometry experiments under the cryogenic environment of helium droplets. The issues associated with the successful development of a nonreactive force field for such clusters are also highlighted.

7.
Phys Chem Chem Phys ; 20(26): 18066-18073, 2018 Jul 14.
Artigo em Inglês | MEDLINE | ID: mdl-29932203

RESUMO

Velocity distributions of neutral water molecules evaporated after collision induced dissociation of protonated water clusters H+(H2O)n≤10 were measured using the combined correlated ion and neutral fragment time-of-flight (COINTOF) and velocity map imaging (VMI) techniques. As observed previously, all measured velocity distributions exhibit two contributions, with a low velocity part identified by statistical molecular dynamics (SMD) simulations as events obeying the Maxwell-Boltzmann statistics and a high velocity contribution corresponding to non-ergodic events in which energy redistribution is incomplete. In contrast to earlier studies, where the evaporation of a single molecule was probed, the present study is concerned with events involving the evaporation of up to five water molecules. In particular, we discuss here in detail the cases of two and three evaporated molecules. Evaporation of several water molecules after CID can be interpreted in general as a sequential evaporation process. In addition to the SMD calculations, a Monte Carlo (MC) based simulation was developed allowing the reconstruction of the velocity distribution produced by the evaporation of m molecules from H+(H2O)n≤10 cluster ions using the measured velocity distributions for singly evaporated molecules as the input. The observed broadening of the low-velocity part of the distributions for the evaporation of two and three molecules as compared to the width for the evaporation of a single molecule results from the cumulative recoil velocity of the successive ion residues as well as the intrinsically broader distributions for decreasingly smaller parent clusters. Further MC simulations were carried out assuming that a certain proportion of non-ergodic events is responsible for the first evaporation in such a sequential evaporation series, thereby allowing to model the entire velocity distribution.

8.
J Phys Chem A ; 122(10): 2792-2800, 2018 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-29451795

RESUMO

The interaction between hydrogen and carbonaceous nanostructures is of fundamental interest in various areas of physical chemistry. In this contribution we have revisited the physisorption of hydrogen molecules and H2 clusters on fullerenes, following a first-principles approach in which the interaction is quantitatively evaluated for the C20 system using high-level electronic structure methods. Relative to coupled cluster data at the level of single, double, and perturbative triple excitations taken as a benchmark, the results for rotationally averaged physisorbed H2 show a good performance of MP2 variants and symmetry-adapted perturbation theory, but significant deviations and basis set convergence issues are found for dispersion-corrected density functional theory. These electronic structure data are fitted to produce effective coarse-grained potentials for use in larger systems such as C60-H2. Using path-integral molecular dynamics, the potentials are also applied to parahydrogen clusters solvated around fullerenes, across the regime where the first solvation shell becomes complete and as a function of increasing temperature. For C60 our findings indicate a sensible dependence of the critical solvation size on the underlying potential. As the temperature is increased, a competition is found between the surface and radial expansions of the solvation shell, with one molecule popping away at intermediate temperatures but getting reinserted at even higher temperatures.

9.
J Chem Phys ; 148(10): 102305, 2018 Mar 14.
Artigo em Inglês | MEDLINE | ID: mdl-29544267

RESUMO

A flexible and polarizable interatomic potential has been developed to model hydrogen clusters interacting with one hydrogen anion, (H2)nH-, in a broad range of sizes n = 1-54 and parametrized against coupled cluster quantum chemical calculations. Using path-integral molecular dynamics simulations at 1 K initiated from the putative classical global minima, the equilibrium structures are found to generally rely on icosahedral shells with the hydrogen molecules pointing toward the anion, producing geometric magic numbers at sizes n = 12, 32, and 44 that are in agreement with recent mass spectrometry measurements. The energetic stability of the clusters is also connected with the extent of vibrational delocalization, measured here by the fluctuations among inherent structures hidden in the vibrational wave function. As the clusters grow, the outer molecules become increasingly free to rotate, and strong finite size effects are also found between magic numbers, associated with more prominent vibrational delocalization. The effective icosahedral structure of the 44-molecule cluster is found to originate from quantum nuclear effects as well, the classical structure showing no particular symmetry.

10.
J Chem Phys ; 149(8): 084308, 2018 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-30193492

RESUMO

Measurement of velocity distributions of evaporated water monomers from small mass- and energy-selected protonated water clusters allows probing the extent of thermalization after excitation of these ultimately small nanodroplets. Electronic excitation of a molecule in the cluster is here induced by a single collision with an argon atom in the keV energy range. The measured velocity distributions of the departing neutral molecules exhibit bimodal shapes with a lower-velocity part consistent with a complete redistribution of the deposited energy in the entire cluster and a higher-velocity contribution corresponding to evaporation before complete energy redistribution. Statistical molecular dynamics calculations reproduce the bimodal shape of the velocity distributions by assuming an initial spreading of the excitation energy among all modes, thereby reproducing the lower velocity contribution of the distribution. By contrast, assuming the deposited energy to be initially localized among the modes of a single molecule leads to calculated distributions with two components whose shape is in accordance with the experimental results. The characteristics and the relative abundance of these two contributions in the velocity distributions obtained are presented and discussed as a function of the number of molecules (n = 2-10) in the ionized nanodroplet H+(H2O) n .

11.
Bull Entomol Res ; 108(6): 765-772, 2018 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-29415782

RESUMO

The potential of the mirid predator Dicyphus hesperus Knight (Heteroptera: Miridae) as a biological control agent of the sweetpotato whitefly, Bemisia tabaci Gennadius (Hemiptera: Aleyrodidae) and the potato psyllid, Bactericera cockerelli Sulcer (Hemiptera: Psyllidae) in tomato was investigated in two experiments. The first experiment focused on the study of the life history traits of D. hesperus when fed on nymphs of the potato psyllid compared with the factitious prey Ephestia kuehniella Zeller (Lepidoptera: Pyrallidae) eggs. Although reproductive and development rates were higher on E. kuehniella eggs, the predator exhibited a good intrinsic rate of natural increase (rm) when feeding on B. cockerelli nymphs (rm: B. cockerelli 0.069 ± 0.0001; E. kuehniella 0.078 ± 0.0001), thus reflecting good potential as a biocontrol agent of this pest. The second experiment focused on the efficacy of D. hesperus as a biocontrol agent of the potato psyllid and the sweetpotato whitefly in a tomato greenhouse. Prey species were offered individually or together in a series of five treatments in greenhouse cages. Results showed that the predator was able to establish and suppress populations of both pests inhabiting tomato plants when pests occurred alone or together. Thus, D. hesperus was demonstrated to be a suitable biocontrol agent of these two important pests that could be used in tomato greenhouses.


Assuntos
Hemípteros/fisiologia , Controle de Insetos/métodos , Características de História de Vida , Controle Biológico de Vetores/métodos , Animais , Dieta , Feminino , Cadeia Alimentar , Heterópteros/fisiologia , Solanum lycopersicum/crescimento & desenvolvimento , Masculino
12.
Ann Oncol ; 28(5): 1145-1151, 2017 May 01.
Artigo em Inglês | MEDLINE | ID: mdl-28453708

RESUMO

BACKGROUND: While next generation sequencing has enhanced our understanding of the biological basis of malignancy, current knowledge on global practices for sequencing cancer samples is limited. To address this deficiency, we developed a survey to provide a snapshot of current sequencing activities globally, identify barriers to data sharing and use this information to develop sustainable solutions for the cancer research community. METHODS: A multi-item survey was conducted assessing demographics, clinical data collection, genomic platforms, privacy/ethics concerns, funding sources and data sharing barriers for sequencing initiatives globally. Additionally, respondents were asked as to provide the primary intent of their initiative (clinical diagnostic, research or combination). RESULTS: Of 107 initiatives invited to participate, 59 responded (response rate = 55%). Whole exome sequencing (P = 0.03) and whole genome sequencing (P = 0.01) were utilized less frequently in clinical diagnostic than in research initiatives. Procedures to identify cancer-specific variants were heterogeneous, with bioinformatics pipelines employing different mutation calling/variant annotation algorithms. Measurement of treatment efficacy varied amongst initiatives, with time on treatment (57%) and RECIST (53%) being the most common; however, other parameters were also employed. Whilst 72% of initiatives indicated data sharing, its scope varied, with a number of restrictions in place (e.g. transfer of raw data). The largest perceived barriers to data harmonization were the lack of financial support (P < 0.01) and bioinformatics concerns (e.g. lack of interoperability) (P = 0.02). Capturing clinical data was more likely to be perceived as a barrier to data sharing by larger initiatives than by smaller initiatives (P = 0.01). CONCLUSIONS: These results identify the main barriers, as perceived by the cancer sequencing community, to effective sharing of cancer genomic and clinical data. They highlight the need for greater harmonization of technical, ethical and data capture processes in cancer sample sequencing worldwide, in order to support effective and responsible data sharing for the benefit of patients.


Assuntos
Estudos de Associação Genética , Neoplasias/genética , Análise Mutacional de DNA , Bases de Dados Genéticas , Predisposição Genética para Doença , Genoma Humano , Humanos , Anotação de Sequência Molecular , Inquéritos e Questionários , Sequenciamento do Exoma
13.
Phys Chem Chem Phys ; 19(3): 1884-1895, 2017 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-28009856

RESUMO

Coarse-grained models developed for polycyclic aromatic hydrocarbons based on the Paramonov-Yaliraki potential have been employed to investigate the finite temperature thermodynamics, out-of-equilibrium dynamics, energy landscapes, and rearrangement pathways of the coronene octamer. Molecular dynamics simulations are used to address the short-time behaviour, diffusion properties, convergence to equilibrium, and dissociation kinetics. A kinetic transition network composed of a connected database of stationary points provides a consistent picture of the complex potential and free energy landscapes, and enables us to describe rearrangements occurring over long time scales and associated thermal properties. Comparison with reference simulations performed with an all-atom description, indicates satisfactory agreement at moderate energies, especially when quadrupole corrections to the intermolecular potential are included. At higher energies, unimolecular evaporation rates are particularly well reproduced by the coarse-grained model. The potential energy landscapes exhibit multiple funnels for all the models, with alternative columnar arrangements competing at low energy. Entropy-driven structural transitions are predicted to involve largely cooperative motion, with entire stacks shifting and rotating around one another. These structural transitions, which were not characterised in earlier parallel tempering Monte Carlo simulations, are well represented by the coarse-grained models, with similar barrier heights but fewer steps.

14.
Bull Entomol Res ; 107(2): 200-207, 2017 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-27573581

RESUMO

The predators Macrolophus basicornis (Stal), Engytatus varians (Distant) and Campyloneuropsis infumatus (Carvalho) consume large numbers of tomato pests such as Bemisia tabaci (Gennadius) and Tuta absoluta (Meyrick). However, they are zoophytophagous and feed on plant parts as well. We evaluated the type and effect of injury caused by nymphs and adults of these mirids on tomato seedlings and fruit in the absence of prey. For each mirid species, seedlings were exposed to groups of 20 nymphs or adults for 72 h, and fruits were exposed for 48 h to groups of four nymphs or adults. Type and the number of injury on stems, petioles and leaflets of tomato seedlings and fruits were recorded after removal of insects. Nymphs and adults of these mirids caused necrotic rings on the leaflets, but no injury was observed on stem and petioles. The necrotic rings on leaflets consisted of blemishes, characterized by feeding punctures surrounded by a yellowish, bleached area. The number of necrotic rings did not exceed one per individual mirid and seedlings developed normally. Nymphs also caused feeding punctures on tomato fruit, but in even lower numbers than on leaflets. Two weeks after the start of the experiment the tomato fruit still looked fresh and feeding punctures had disappeared. Adults did not cause any injury to tomato fruit. The results indicate that nymphs and adults of these zoophytophagous mirids cause little injury to tomato seedlings and fruit, even when present in high densities and in the absence of prey, making them interesting candidates for biological control.


Assuntos
Herbivoria , Heterópteros/fisiologia , Solanum lycopersicum/fisiologia , Animais , Feminino , Cadeia Alimentar , Frutas/fisiologia , Heterópteros/crescimento & desenvolvimento , Masculino , Ninfa/crescimento & desenvolvimento , Ninfa/fisiologia , Controle Biológico de Vetores , Folhas de Planta/fisiologia
15.
Phys Chem Chem Phys ; 18(20): 13736-40, 2016 05 18.
Artigo em Inglês | MEDLINE | ID: mdl-27055581

RESUMO

Clusters of polycyclic aromatic hydrocarbons (PAHs) are essential components of soot and may concentrate a significant fraction of carbon matter in the interstellar medium. In this contribution, coarse-grained potentials are parameterized using all-atom reference data to model PAH molecules, such as coronene (C24H12) or circumcoronene (C54H18), and their aggregates. Low-energy structures of pure coronene or circumcoronene clusters obtained using basin-hopping global optimization are found to agree with atomistic results, and consist of finite 1D columnar motifs, sometimes juxtaposed in larger clusters. The structures are only weakly perturbed when quadrupolar interactions are included. π-Stacking also dominates in binary coronene/circumcoronene aggregates, although intriguing motifs are predicted in which one or more molecules are sandwiched between the other PAH species. The coarse-grained model is also extended to account for interaction with a flat graphitic substrate. In this case, binding is stronger with the substrate than with other molecules, and the PAHs are predicted to arrange into a flat triangular monolayer.

16.
J Phys Chem A ; 120(10): 1727-36, 2016 Mar 17.
Artigo em Inglês | MEDLINE | ID: mdl-26890583

RESUMO

Using path-integral molecular dynamics simulations and two quantum-mechanical-based force fields, we have investigated the conformational stability of dimers of a polycyclic aromatic hydrocarbon, perylene (C20H12), produced under typical experimental conditions of successive pick-up under helium nanodroplet environment. The most stable configurations are found to be of the stacked form with different relative orientations of the main molecular axes, perpendicular or T-shaped dimers being energetically much disfavored; however, in the presence of helium our simulations suggest that the time for rearrangement and π-stacking may be rather long and exceed hundreds of picoseconds. In addition, highly metastable dimers that are stacked but with a helium monolayer sandwiched between the two molecules are also found as likely products upon successive pickup. This stabilization occurs owing to the stronger localization of the helium atoms facing the aromatic rings, which is further enhanced in the dimer. The implications of the present results are discussed in the perspective of possible identification by spectroscopic methods.

17.
J Phys Chem A ; 120(15): 2380-9, 2016 Apr 21.
Artigo em Inglês | MEDLINE | ID: mdl-27035034

RESUMO

It was recently suggested that 2-aminooxazole (AO) could contribute to the formation of RNA nucleotides on primitive earth. In this article we have considered by means of computational modeling the influence of microhydration on the structural and spectral properties of this potential prebiotic molecule. The stable structures of AO(H2O)n were obtained first by sampling the potential energy landscapes of clusters containing up to n = 20 water molecules, using a simple but reasonably accurate force field and replica-exchange molecular dynamics simulations. Through reoptimization using an explicit description of electronic structure at the level of density functional theory with the M06-2X functional, the formation energies, ionization energies and electron affinities were determined in the vertical and adiabatic treatments, as well as vibrational and optical spectra covering the far-IR, mid-IR, and lower part of the UV ranges. The results generally show a clear segregation between the aminooxazole solute and the water molecules, a water cluster being formed near the nitrogen and amino group side leaving the hydrocarbon side dry even at temperatures corresponding to the liquid state. The spectral signatures generally concur and show distinct contributions of the solute and solvent, spectral shifts to lower energies being in agreement with earlier calculations in bulk solvent. We have also investigated the importance of microhydration on the charge transfer cross section upon collision with a proton, thereby extending an earlier investigation on the bare AO molecule. The presence of water molecules generally reduces the propensity for charge transfer at small sizes, but the influence of the solvent steadily decreases in larger droplets.


Assuntos
Simulação de Dinâmica Molecular , Oxazóis/química , Prótons , Teoria Quântica , Solventes/química , Temperatura , Termodinâmica
18.
J Chem Phys ; 144(22): 224302, 2016 Jun 14.
Artigo em Inglês | MEDLINE | ID: mdl-27306002

RESUMO

This work theoretically examines the progressive coating of planar polycyclic aromatic hydrocarbon (PAH) molecules ranging from benzene to circumcoronene (C54H18) by para-hydrogen and ortho-deuterium. The coarse-grained Silvera-Goldman potential has been extended to model the interactions between hydrogen molecules and individual atoms of the PAH and parametrized against quantum chemical calculations for benzene-H2. Path-integral molecular dynamics simulations at 2 K were performed for increasingly large amounts of hydrogen coating the PAH up to the first solvation shell and beyond. From the simulations, various properties were determined such as the size of the first shell and its thickness as well as the solvation energy. The degree of delocalization was notably quantified from an energy landscape perspective, by monitoring the fluctuations among inherent structures sampled by the trajectories. Our results generally demonstrate a high degree of localization owing to relatively strong interactions between hydrogen and the PAH, and qualitatively minor isotopic effects. In the limit of large hydrogen amounts, the shell size and solvation energy both follow approximate linear relations with the numbers of carbon and hydrogen in the PAH.

19.
J Chem Phys ; 145(8): 084304, 2016 Aug 28.
Artigo em Inglês | MEDLINE | ID: mdl-27586919

RESUMO

The coating of various fullerenes by para-hydrogen and ortho-deuterium molecules has been computationally studied as a function of the solvent amount. Rotationally averaged interaction potentials for structureless hydrogen molecules are employed to model their interaction with neutral or charged carbonaceous dopants containing between 20 and 240 atoms, occasionally comparing different fullerenes having the same size but different shapes. The solvation energy and the size of the first solvation shell obtained from path-integral molecular dynamics simulations at 2 K show only minor influence on the dopant charge and on the possible deuteration of the solvent, although the shell size is largest for ortho-D2 coating cationic fullerenes. Nontrivial finite size effects have been found with the shell size varying non-monotonically close to its completion limit. For fullerenes embedded in large hydrogen clusters, the shell size and solvation energy both follow linear scaling with the fullerene size. The shell sizes obtained for C60 (+) and C70 (+) are close to 49 and 51, respectively, and agree with mass spectrometry experiments.

20.
Bull Entomol Res ; 106(4): 502-11, 2016 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-27121181

RESUMO

Necremnus tutae is native to the Mediterranean region where it has been observed in greenhouses parasitizing the invasive Tuta absoluta on tomato. The objective of the present study was to determine whether augmentative releases of N. tutae can improve existing biological control of T. absoluta based on predation by Nesidicoris tenuis. Two experiments were carried out, of which the first evaluated different N. tutae release rates (1 and 2 N. tutae m-2 week-1). The parasitoid reduced plant and fruit damage, especially at the higher rate. However, such reduction was considered insufficient given the large numbers of parasitoids needed and still unacceptable level of fruit damage. The second experiment focused on combining the most efficient rate of N. tutae of those evaluated during the first experiment, with the pre- and post-planting release of N. tenuis and supplemental additions of Ephestia kuehniella eggs. Addition of N. tutae decreased leaf damage by T. absoluta regardless the release method for N. tenuis, but the pre-plant release of N. tenuis alone was sufficient to prevent fruit damage by T. absoluta. This suggested that the addition of N. tutae may not be necessary to obtain satisfactory control of T. absoluta following pre-plant application of N. tenuis, although different options for using N. tutae in commercial crops may still be possible.


Assuntos
Interações Hospedeiro-Parasita , Mariposas/parasitologia , Controle Biológico de Vetores/métodos , Vespas/fisiologia , Animais , Herbivoria , Espécies Introduzidas , Solanum lycopersicum , Mariposas/fisiologia
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