Self-assembly mechanism of PEG-b-PCL and PEG-b-PBO-b-PCL amphiphilic copolymer micelles in aqueous solution from coarse grain modeling

We followed the self-assembly of high-molecular weight MePEG- b -PCL (poly(methyl ethylene glycol)-block-poly(ε-caprolactone)) diblock and MePEG- b -PBO- b -PCL (poly(methyl ethylene glycol)-block-poly(1,2-butylene oxide)-block-poly(ε-caprolactone)) into micelles using molecular dynamics simulation with a coarse grain (CG) force field based on quantum mechanics (CGq FF). The triblock polymer included a short poly(1,2-butylene oxide) (PBO) at the hydrophilic-hydrophobic interface of these systems. Keeping the hydrophilic length fixed (MePEG₄₅), we considered 250 chains in which the hydrophobic length changed from PCL₄₄ or PBO₆- b -PCL₄₃ to PCL₆₂ or PBO₉- b -PCL₆₁. The polymers were solvated in explicit water for 2 μs of simulations at 310.15 K. We found that the longer diblock system undergoes a morphological transition from an intermediate rod-like micelle to a prolate-sphere, while the micelle formed from the longer triblock system is a stable rod-like micelle. The two shorter diblock and triblock systems show similar self-assembly processes, both resulting in slightly prolate-spheres. The dynamics of the self-assembly is quantified in terms of chain radius of gyration, shape anisotropy, and hydration of the micelle cores. The final micelle structures are analyzed in terms of the local density components. We conclude that the CG model accurately describes the molecular mechanisms of self-assembly and the equilibrium micellar structures of hydrophilic and hydrophobic chains, including the quantity of solvent trapped inside the micellar core.     

Calculus of variations as a basic tool for modelling of reaction paths and localisation of stationary points on potential energy surfaces

ABSTRACT

The theory of calculus of variations is a mathematical tool which is widely used in different scientific areas in particular in physics and chemistry. This theory is strongly related with optimisation. In fact the former seeks to optimise an integral related with some physical magnitude over some space to an extremum by varying a function of the coordinates. On the other hand, reaction paths and potential energy surfaces, in particular their stationary points, are the basis of many chemical theories, in particular reactions rate theories. We present a review where it is gathered together the variational nature of many types of reaction paths: steepest descent, Newton trajectories, artificial force induced reaction (AFIR) paths, gradient extremals, and gentlest ascent dynamics (GAD) curves. The variational basis permits to select the best optimisation technique in order to locate important theoretical objects on a potential energy surface.     

基于Rietveld精修方法解析Bi2O3的原子热振动

三氧化二铋(Bi₂O₃)是氧离子导电体,为了获得它的原子热振动各向同性温度因子,对该粉末晶体进行X射线衍射实验,建立了晶体结构模型,利用Rietveld 精修方法的RIETAN-2000 程序对所得实验结果进行了晶体结构精修,通过最大熵方法(MEM)解析得到了粉末晶体的等高电子密度分布三维(3D) 和二维(2D)可视化图谱。结果表明,各原子Bi₍₁₎、Bi₍₂₎、O₍₁₎、O₍₂₎和O₍₃₎的原子热振动各向同性温度因子分别为0.004 938 nm²、0.004 174 nm²、0.007 344 nm²、0.007 462 nm²、和0.007 857 nm²,等高电子密度分布的可视化,进一步验证了晶体结构模型和原子位置的准确性,这些参数对研究晶体材料的热性质具有一定参考意义。     

Investigation of 500 keV Si ion induced surface structuring of Ni and Ti for enhancement of field emission properties

The present paper reports the investigation of surface morphology, elemental composition, phase changes and field emission properties of Si ion irradiated nickel (Ni) and titanium (Ti). The Ni and Ti targets have been irradiated with 500 keV Si ions generated by Pelletron accelerator at various fluences ranging from 6.9 × 10¹³ to 77.1 × 10¹³ ions/cm². Stopping range of ions in matter analysis revealed higher values of electronic stopping and sputtering yield for Ni as compared with Ti. For both irradiated metals, electronic energy loss dominant over the nuclear stopping. The growth of induced surface structures have been analysed by using field emission scanning electron microscopy (FESEM) analysis. In case of Ni, as the ion fluence increases from 6.9 × 10¹³ to 65.8 × 10¹³ ions/cm², the formation of spherical particulates, agglomers and sputtering is observed. Although in the case of Ti, with the increase of Si ion fluence from 11.6 × 10¹³ to 77.1 × 10¹³ ions/cm², the formation of irregular-shaped particulates along with crater and sputtered channels is observed. X-ray diffraction (XRD) analysis shows that no new phase is identified. However, a significant increase in peak intensity is observed with increasing ion fluence. The variation in crystallite size and dislocation line density is also observed as a function of Si ion fluence. Fourier transform infrared spectroscopy analysis shows that no bands are formed after the Si ion irradiation. Field emission properties of ion-structured Ni and Ti are well correlated with the growth of surface structures observed by SEM and dislocation line density evaluated by XRD analysis.     

Development of models for prediction of the antioxidant activity of derivatives of natural compounds

Antioxidants are important for maintaining the appropriate balance between oxidizing and reducing species in the body and thus preventing oxidative stress. Many natural compounds are being screened for their possible antioxidant activity. It was found that a mushroom pigment Norbadione A, which is a pulvinic acid derivative, shows an antioxidant activity; the same was found for other pulvinic acid derivatives and structurally related coumarines. Based on the results of in vitro studies performed on these compounds as a part of this study quantitative structure–activity relationship (QSAR) predictive models were constructed using multiple linear regression, counter-propagation artificial neural networks and support vector regression (SVR). The models have been developed in accordance with current QSAR guidelines, including the assessment of the models applicability domains. A new approach for the graphical evaluation of the applicability domain for SVR models is suggested. The developed models show sufficient predictive abilities for the screening of virtual libraries for new potential antioxidants.     

Pesticidal potential of some wild plant essential oils against grain pests Tribolium castaneum (Herbst, 1797) and Aspergillus flavus (Link, 1809)

The red flour beetle, Tribolium castaneum, and the mold Aspergillus flavus are well known threats of stored grain commodities, causing nutritional loss and poisoning of stored products, respectively. T. castaneum has developed resistance against most insecticides, leading to the use of extensive amounts of synthetic insecticides to protect stored grains. Synthetic pesticides not only toxify the environment but also cause serious health issues in humans using pesticide treated grains. This study aimed to identify plant-based natural pesticides to control T. castaneum and A. flavus. Essential oils were extracted from fresh aerial parts of Chenopodium ambrosioides, Conyza sumatrensis, Erigeron canadensis, and Tagetes minuta through steam distillation and investigated for insecticidal and anti-fungal activities against adult T. castaneum and A. flavus, respectively. GC–MS analysis of C. sumatrensis revealed the presence of 37.7% cis-lachnophyllum ester, 13.4% germacrene D, and 21.6% limonene, whereas in E. canadensis the major compounds were limonene, germacrene D, and cis-lachnophyllum ester (43.4%, 12.9% and 5.9%, respectively). In bioassays with treated grain, C. sumatrensis and E. canadensis essential oils exhibited excellent toxicity against adult T. castaneum with LD₅₀ of 3.7 and 5.6 mg per 10 g grains whereas in a fumigation bioassay they showed LD₅₀ of 6.6 and 10.6 mg/L, respectively. The essential oils extracted from C. ambrosioides and E. canadensis exhibited good anti-fungal activity against A. flavus. Our findings suggest that essential oils of C. sumatrensis and E. canadensis can play an important role in protecting stored grains from T. castaneum and A. flavus contamination.     

Maximizing H‐Colorings of Connected Graphs with Fixed Minimum Degree

For graphs G and H , an H‐coloring of G is a map from the vertices of G to the vertices of H that preserves edge adjacency. We consider the following extremal enumerative question: for a given H , which connected n‐vertex graph with minimum degree δ maximizes the number of H‐colorings? We show that for nonregular H and sufficiently large n , the complete bipartite graph is the unique maximizer. As a corollary, for nonregular H and sufficiently large n the graph is the unique k‐connected graph that maximizes the number of H‐colorings among all k‐connected graphs. Finally, we show that this conclusion does not hold for all regular H by exhibiting a connected n‐vertex graph with minimum degree δ that has more ‐colorings (for sufficiently large q and n ) than .     

On the construction of non-affine jump-diffusion models

We describe a method for construction of jump analogues of certain one-dimensional diffusion processes satisfying solvable stochastic differential equations. The method is based on the reduction of the original stochastic differential equations to the ones with linear diffusion coefficients, which are reducible to the associated ordinary differential equations, by using the appropriate integrating factor processes. The analogues are constructed by means of adding the jump components linearly into the reduced stochastic differential equations. We illustrate the method by constructing jump analogues of several diffusion processes and expand the notion of market price of risk to the resulting non-affine jump-diffusion models.     

Utility maximization problem with random endowment and transaction costs: when wealth may become negative

In this article, we study the problem of maximizing expected utility from the terminal wealth with proportional transaction costs and random endowment. In the context of the existence of consistent price systems, we consider the duality between the primal utility maximization problem and the dual one, which is set up on the domain of finitely additive measures. In particular, we prove duality results for utility functions supporting possibly negative values. Moreover, we construct a shadow market by the dual optimal process and consider the utility-based pricing for random endowment.