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To manage intra-fractional motions, recent developments in tomotherapy enable a unique capability of adjusting MLC/jaw to track the moving target based on the intra-fractional motions detected by sequential monoscopic imaging. In this study, we evaluated the effectiveness of motion compensation with a realistic imaging rate for prostate stereotactic body radiotherapy (SBRT). The obtained results will guide optimizing treatment parameters and image-guided radiation therapy (IGRT) in tomotherapy using this approach.Ten retrospective prostate cases with actual prostate motion curves previously recorded through the Calypso system were used in this study. Based on the recorded peak-to-peak motion, these cases represented either large ( 5 mm) or median (≤ 5 mm) intra-fractional prostate motions. All the cases were re-planned on tomotherapy using 35 Gy/5 fractions SBRT regimen and three different jaw settings of 1 cm static, 2.5 cm static, and 2.5 cm dynamic jaw. Two motion compensation methods were evaluated: a complete compensation that adjusted the jaw and MLC every 0.1 s (the same rate as the Calypso motion trace), and a realistic compensation that adjusted the jaw and MLC at an average imaging interval of 6 s from sequential monoscopic images. An in-house 4D dose calculation software was then applied to calculate the dosimetric outcomes from the original motion-free plan, the motion-contaminated plan, and the two abovementioned motion-compensated plans. During the process, various imaging rates were also simulated in one case with unusually large motions to quantify the impact of the KV-imaging rate on the effectiveness of motion compensation.The effectiveness of motion compensation was evaluated based on the PTV coverage and OAR sparing. Without any motion-compensation, the PTV coverage (PTV V100%) of patients with large prostate motions decreased remarkably to 55%-82% when planning with the 1 cm jaw but to a less level of 67-94% with the 2.5 cm jaw. In contrast, motion compensation improved the PTV coverage (92%) when combined with the 2.5 cm jaw, but less effective, around 75%-94%, with the 1 cm jaw. For OAR sparing, the bladder D1cc, bladder D10cc, and rectum D1cc all increased in the motion-contaminated plans. Motion compensation improved OAR sparing to the equivalent level of the original motion-free plans. For patients with median prostate motion, motion-induced degradation in PTV coverage was only observed when planning with the 1 cm jaw. After motion compensation, the PTV coverage improved to better than 94% for all three jaw settings. Additionally, the effectiveness of motion compensation depends on the imaging rate. Motion compensation with a typical rate of two KV images per gantry rotation effectively reduces motion-induced dosimetric uncertainties. However, a higher imaging rate is recommended when planning with a 1 cm jaw for patients with large motions.Our results demonstrated that the performance of sequential monoscopic imaging-guided motion compensation on tomotherapy depends on the amplitude of intra-fractional prostate motion, the plan parameter settings, especially jaw setting, gantry rotation, and the imaging rate for motion compensation. Creating a patient-specific imaging guidance protocol is essential to balance the effectiveness of motion compensation and achievable imaging rate for intra-fractional motion tracking.

The asymmetric total synthesis of three lindenane sesquiterpenoid oligomers, shizukaol J, trichloranoid C and trishizukaol A, has been accomplished concisely in 15, 16 and 18 longest linear steps, respectively. The expeditious construction of molecular architectures was facilitated by Nelson's catalytic asymmetric ketene-aldehyde cycloaddition, a sequence of allylic alkylation/reduction/acidic cyclization to forge a lactone, and a double aldol condensation cascade to construct the 5/6 bicyclic system. Diastereoselective nucleophilic substitution promoted by a phase transfer catalyst constructed the C

Z-scheme photocatalytic systems are an ideal band alignment structure for photocatalysis because of the high separation efficiency of photo-induced carriers while simultaneously preserving the strong reduction activity of electrons and oxidation activity of holes. However, the design and construction of Z-scheme photocatalysts is challenging because of the need for appropriate energy band alignment and built-in electric field. Here, we propose a novel approach to a Z-scheme photocatalytic system using density functional theory calculations with the HSE06 hybrid functional. The undesirable type-I g-C3 N4 /MoSe2 heterojunction is transformed into a direct Z-scheme system through boron doping of g-C3 N4 (B-doped C3 N4 /MoSe2 ). Detailed analysis of the total and partial density of states, work functions and differential charge density distribution of the B-doped C3 N4 /MoSe2 heterojunction shows the proper band alignment and existence of a built-in electric field at the interface, with the direction from g-C3 N4 to MoSe2 , demonstrating a direct Z-scheme heterojunction. Further investigation on the absorption spectra reveals a large enhancement of the light absorption efficiency after boron doping. The results consistently confirm that electronic structures and photocatalytic performance can be effectively manipulated by a facile boron doping. Modulating the band alignment of heterojunctions in this way provides valuable insights for the rational design of highly efficient heterojunction-based photocatalytic systems.

The blood-brain barrier (BBB) as a part of absorption protects the central nervous system by separating the brain tissue from the bloodstream. In recent years, BBB permeability has become a critical issue in chemical ADMET prediction, but almost all models were built using imbalanced data sets, which caused a high false-positive rate. Therefore, we tried to solve the problem of biased data sets and built a reliable classification model with 2358 compounds. Machine learning and resampling methods were used simultaneously for the refinement of models with both 2 D molecular descriptors and molecular fingerprints to represent the chemicals. Through a series of evaluation, we realized that resampling methods such as Synthetic Minority Oversampling Technique (SMOTE) and SMOTE+edited nearest neighbor could effectively solve the problem of imbalanced data sets and that MACCS fingerprint combined with support vector machine performed the best. After the final construction of a consensus model, the overall accuracy rate was increased to 0.966 for the final external data set. Also, the accuracy rate of the model for the test set was 0.919, with an excellent balanced capacity of 0.925 (sensitivity) to predict BBB-positive compounds and of 0.899 (specificity) to predict BBB-negative compounds. Compared with other BBB classification models, our models reduced the rate of false positives and were more robust in prediction of BBB-positive as well as BBB-negative compounds, which would be quite helpful in early drug discovery.

Comprehensive experimental quantification and mapping of the aggregation and dispersion state of engineered nanoparticles (NPs) in the presence of humic substances is a great challenge. Dissipative particle dynamic (DPD) simulation was adopted to investigate the aggregation and dispersion mechanisms of NPs in the presence of a humic substance analog. Twelve different types of NPs including 2 metal-based NPs, 7 metal oxide-based NPs, and 3 carbon-based NPs in pure water (pH 3.0) and algae medium (pH 8.0) in the presence of a humic substance analogy were selected for experimental verification of the DPD simulation results. In agreement with results obtained with dynamic light scattering and phase analysis light scattering techniques, the simulations demonstrated that the presence of humic substances reduced the aggregation extent of the NPs. The DPD simulations showed that the stability and dispersity of the NPs increased first, and then decreased with increasing concentrations of humic substances. Moreover, there existed a concentration of humic substances where the NPs became more stable and more dispersed, which was experimentally verified in the case of all the NPs in the pure water and in the algae medium. Furthermore, theory and simulation indicate that both hydrophobic and hydrogen interaction play an important role in controlling the formation of NP aggregates in the presence of humic substances. Electrostatic interaction and steric repulsion are the main mechanisms underlying the effects of humic substances on the aqueous dispersion stability of NPs. Environ Toxicol Chem 2018;37:1024-1031. © 2017 SETAC.

g-C3 N4 /CdS heterojunctions are potential photocatalysts for hydrogen production but their traditional type-II configuration generally leads to weak oxidative and reductive activity. How to construct the novel Z-scheme g-C3 N4 /CdS counterparts to address this issue remains a great challenge in this field. In this work, a new direct Z-scheme heterojunction of defective g-C3 N4 /CdS is designed by introducing cyano groups (NC-) as the active bridge sites. Experimental observations in combination with density functional theory (DFT) calculations reveal that the unique electron-withdrawing feature of cyano groups in the defective g-C3 N4 /CdS heterostructure can endow this photocatalyst with numerous advantageous properties including high light absorption ability, strong redox performance, satisfactory charge separation efficiency, and long lifetime of charge carriers. Consequently, the resultant photocatalytic system exhibits more active performance than CdS and g-C3 N4 under visible light and reaches an excellent hydrogen evolution rate of 1809.07 µmol h-1 g-1 , which is 6.09 times higher than pristine g-C3 N4 . Moreover, the defective g-C3 N4 /CdS photocatalyst maintains good stability after 40 h continuous test. This work provides new insights into design and construction of Z-scheme heterojunctions for regulating the visible-light-induced photocatalytic activity for H2 evolution.

Pine wilt disease (PWD) is considered as the most destructive forest-invasive alien species in China. We measured gas exchange parameters and foliar carbon isotope ratios (δ13C) of different infection phases of Masson pine in order to investigate the effect of Bursaphelenchus xylophilus infection on photosynthetic responses and resource-use efficiency. The results showed that net photosynthetic rate (Pn), transpiration rate (T), stomatal conductance (gs), and internal CO 2 concentrations (Ci) decreased in the infested trees at photosynthetic photon flux density (PPFD) levels from 0 to 2,000 μmol m-2 s-1 compared with controls. The maximum net photosynthetic rate (Pmax) was significantly declined in the infected trees than in controls (p < .05). There also exist significant differences in dark respiration rate (Rd) among different infection phases (p < .05), but the value is highest in the middle infection phase, followed by the control and then the terminal infection phase. This indicates that Pinus massoniana plants need to consume more photosynthetic products during the middle infection phase in order to defend against pine sawyer beetle feeding and PWD infection. Isotopic analysis revealed a significant decrease of the foliar δ13C (p < .05), as much as 2.5‰ lower in the infected trees. The mean leaf N content was about 12.94% less in the middle infection phase and 27.06% less in the terminal infection phase, causing a significant increase of the foliar C:N ratio in infested trees. Both of the net photosynthetic rates and foliar δ13C were linearly correlated with the foliar N content. We also found a significant decrease (p < .05) of resource-use efficiency in PWD-induced P. massoniana plants, which can be attributed to the closure of stomatal pores and the inactivation or loss of both Rubisco and other key Calvin cycle enzymes. This study highlights the impact of photosynthetic characteristics, foliar carbon isotope ratios, and resource-use efficiency of PWD-induced trees, which can help identify PWD infestations at the photosynthetic and physiological levels so as to better facilitate management actions.

High-performance GeTe-based thermoelectrics have been recently attracting growing research interest. Here, an overview is presented of the structural and electronic band characteristics of GeTe. Intrinsically, compared to low-temperature rhombohedral GeTe, the high-symmetry and high-temperature cubic GeTe has a low energy offset between L and sigma points of the valence band, the reduced direct bandgap and phonon group velocity, and as a result, high thermoelectric performance. Moreover, their thermoelectric performance can be effectively enhanced through either carrier concentration optimization, band structure engineering (bandgap reduction, band degeneracy, and resonant state engineering), or restrained lattice thermal conductivity (phonon velocity reduction or phonon scattering). Consequently, the dimensionless figure of merit, ZT values, of GeTe-based thermoelectric materials can be higher than 2. The mechanical and thermal stabilities of GeTe-based thermoelectrics are highlighted, and it is found that they are suitable for practical thermoelectric applications except for their high cost. Finally, it is recognized that the performance of GeTe-based materials can be further enhanced through synergistic effects. Additionally, proper material selection and module design can further boost the energy conversion efficiency of GeTe-based thermoelectrics.

Simulations at multiple levels were performed to investigate the aqueous adsorption of phthalate esters (PAEs) on carbon nanoparticles and to find the competitive effect of a low molecular weight natural organic acid (benzoic acid) on the adsorption process. Six PAEs of varying alkyl side chain lengths and three carbon-based nanomaterials including a single-walled carbon nanotube (SWNT), double-walled carbon nanotube (DWNT), and graphene (G) were studied. Results showed that the adsorption energies calculated using density functional theory increase with increasing length of the PAE alkyl chain. G exhibits higher adsorption capacity for the PAEs than SWNT and DWNT. The absolute adsorption energies of these systems also display a positive linear correlation with the hydrophobicity of the PAE molecules. Molecular dynamics simulations indicate that the presence of neutral/anionic benzoic acid in water alleviates the PAE adsorption. Furthermore, anionic benzoic acid exerts more impact on the PAE adsorption than the neutral form.

The present study investigated how humic substances (HS) modify the aquatic toxicity of silver nanoparticles (AgNPs) as these particles agglomerate in water and interact with HS. An alga species (Raphidocelis subcapitata), a cladoceran species (Chydorus sphaericus), and a freshwater fish larva (Danio rerio), representing organisms of different trophic levels, were exposed to colloids of the polyvinylpyrrolidone-coated AgNPs in the presence and absence of HS. Results show that the presence of HS alleviated the aquatic toxicity of the AgNP colloids to all the organisms in a dose-dependent manner. The particle size distribution of the AgNPs' colloidal particles shifted to lower values due to the presence of HS, implying that the decrease in the toxicity of the AgNP colloids cannot be explained by the variation of agglomeration size. The surface charge of the AgNPs was found to be more negative in the presence of high concentrations of HS, suggesting an electrostatic barrier by which HS might limit interactions between particles and algae cells; indeed, this effect reduced the algae toxicity. Observations on silver ions (Ag(+)) release show that HS inhibit AgNP dissolution, depending on the concentrations of HS. When toxic effects were expressed as a function of each Ag-species, toxicity of the free Ag(+) was found to be much higher than that of the agglomerated particles.

Traditionally, administered mass is used to describe doses of conventional chemical substances in toxicity studies. For deriving toxic doses of nanomaterials, mass and chemical composition alone may not adequately describe the dose, because particles with the same chemical composition can have completely different toxic mass doses depending on properties such as particle size. Other dose metrics such as particle number, volume, or surface area have been suggested, but consensus is lacking. The discussion regarding the most adequate dose metric for nanomaterials clearly needs a systematic, unbiased approach to determine the most appropriate dose metric for nanomaterials. In the present study, the authors propose such an approach and apply it to results from in vitro and in vivo experiments with silver and silica nanomaterials. The proposed approach is shown to provide a convenient tool to systematically investigate and interpret dose metrics of nanomaterials. Recommendations for study designs aimed at investigating dose metrics are provided.

Increased use and production of carbon nanomaterials (e.g., fullerene C60) and ionic liquids (ILs) may result in their concomitant releases into the environment. Inevitably there will be interactions between carbon nanoparticles (CNPs) and ILs. However, experimental data on the interaction of CNPs with ILs are not readily available, and the mechanism behind the interactions is still elusive. To contribute to an understanding of the molecular interactions established between CNPs and ILs, theoretical investigations at multiple levels were performed to determine the interactions of C60 with 6 different imidazolium-based ILs. The results indicate that C60 mainly interacts with the IL molecules through the van der Waals, π–cation, and hydrophobic interactions. Mulliken population analysis suggests that charge transfer occurs from the IL to C60 during the C60–IL interaction. The self-diffusion coefficient (D) of C60 in [C60 + IL] systems reaches the maximum in the case of moderate C60–IL interaction (interaction energy, EINT), implying that in this case a good dispersion of an agglomerate species of C60 is obtained. The D value of C60 in [C60 + IL + water] systems increases with an increase of the EINT, implying that the presence of ILs can play an important role in the aqueous dispersion of the C60 agglomerate. Environ Toxicol Chem 2014;33:1802–1808. © 2014 SETAC

BACKGROUND Terpenoids are major components of carotenoids, limonoids and aromas in citrus fruits, resulting in fruit coloration, bitterness and aroma. In this study the carotenoid, limonoid and volatile profiles of red-flesh Chuhong pummelo (CH) and pale green-flesh Feicui pummelo (FC) were investigated by HPLC and GC/MS. RESULTS Large differences were found in constituents of carotenoids and limonoids in juice sacs and flavedo and of aromas in flavedo of the two pummelos. For carotenoids in juice sacs, CH contained 57 times the amount in FC, mainly all-trans-lycopene and phytoene, whereas in flavedo it contained only 25% of that in FC, the latter showing a high proportion of β-carotene and other chloroplastic carotenoids. In comparison with FC, limonin and nomilin aglycone production was boosted in juice sacs of CH while being almost absent in flavedo. For volatiles in flavedo, the total amount was significantly higher in CH. PCA suggested that germacrene-type sesquiterpenoids, etc. were principal in distinguishing volatile profiles of the two pummelos. CONCLUSION The data showed a different tissue-biased pattern of carotenoid and limonoid aglycone synthesis in pummelos with different flesh color, and the possible independently regulated synthesis of those metabolites in different fruit tissues. Furthermore, decreased carotenoid and limonoid aglycone production accompanied by increased accumulation of volatile terpenoids in flavedo of red-flesh CH was identified, indicating that a total capacity or a balance of production of various terpenoids might exist in pummelo fruit tissues. It was also suggested that substrate concentration is not the key factor affecting product concentrations during the synthesis of monoterpene derivatives. © 2014 Society of Chemical Industry

The wide uses of nanosilver (nAg) have resulted in concerns regarding ecotoxicity to aquatic organisms. Some previous studies have found that the toxicity of nAg is due to the nanoparticles themselves, while others have found that ionic silver (Ag+) released by nAg particles plays an important role. In the present study, the authors quantitatively evaluated the relative contribution of nAg particles and Ag+ to the toxicity to three aquatic organisms of different trophic levels, including an algal species (Raphidocelis subcapitata), a cladoceran species (Chydorus sphaericus), and a freshwater fish larva (Danio rerio). A bare and a polyvinylpyrrolidone (PVP)–coated nAg as well as a monodispersed nAg with a dispersant (DIS-nAg) were examined. The toxicity of the nAg in the form of colloids decreased in the order DIS-nAg > PVP-nAg > Bare-nAg for all three trophic aquatic organisms (in terms of median effect concentration). The DIS-nAg had the highest and Bare-nAg the lowest concentration of free Ag+, implying that free Ag+ cannot be neglected in explaining the toxicity of nAg colloids. Furthermore, the contribution of free Ag+ to the toxicity of nAg colloids for R. subcapitata was the highest but for D. rerio the lowest, implying that the organisms tested have different accumulation abilities for Ag+ or nAg particles. Environ. Toxicol. Chem. 2012; 31: 2408–2413. © 2012 SETAC

We propose an approximate form of the exchange-correlation energy functional for the Gutzwiller density functional theory. It satisfies certain physical constraints in both weak and strong electron correlation limits. We benchmark the Gutzwiller density functional approximation in the hydrogen systems, where the static correlation error is shown to be negligible. The good transferability is demonstrated by applications to the hydrogen molecule and some crystal structures. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2012

We performed first-principles calculations to study the structure and stability of Si70 cluster. The results from the density functional theory calculation with the Becke–Lee–Yang–Parr and B3LYP exchange-correlation functionals suggest that a diamond-like Si70 isomer is the most stable structure, in contrast to endohedral fullerenes of Si70. On the other hand, an endohedral fullerene of Si16@Si54 was found to be slightly lower in energy than the diamond-like Si70 if the Predew–Burke–Ernzerhof functional is used. Our calculation results suggest that around n = 70, the endohedral fullerene and diamond-like isomer are expected to be competitive. The calculated IR vibration spectra, ionization potential, and inverse mobilities were also calculated and discussed. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011

Tailoring molybdenum selenide electrocatalysts with tunable phase and morphology is of great importance for advancement of hydrogen evolution reaction (HER). In this work, phase- and morphology-modulated N-doped MoSe2 /TiC-C shell/core arrays through a facile hydrothermal and postannealing treatment strategy are reported. Highly conductive TiC-C nanorod arrays serve as the backbone for MoSe2 nanosheets to form high-quality MoSe2 /TiC-C shell/core arrays. Impressively, continuous phase modulation of MoSe2 is realized on the MoSe2 /TiC-C arrays. Except for the pure 1T-MoSe2 and 2H-MoSe2 , mixed (1T-2H)-MoSe2 nanosheets are achieved in the N-MoSe2 by N doping and demonstrated by spherical aberration electron microscope. Plausible mechanism of phase transformation and different doping sites of N atom are proposed via theoretical calculation. The much smaller energy barrier, longer HSe bond length, and diminished bandgap endow N-MoSe2 /TiC-C arrays with substantially superior HER performance compared to 1T and 2H phase counterparts. Impressively, the designed N-MoSe2 /TiC-C arrays exhibit a low overpotential of 137 mV at a large current density of 100 mA cm-2 , and a small Tafel slope of 32 mV dec-1 . Our results pave the way to unravel the enhancement mechanism of HER on 2D transition metal dichalcogenides by N doping.

A new family of BeB2 structures, where the B atoms form hexagonal layers intercalated by Be atoms is predicted using a generic algorithm method and first-principle DFT calculations.