Panisuffrutin A,a highly degraded seco-triterpene derivative from Paeonia suffruticosa var. papaveracea (Andr.) Kerner

Panisuffrutin A (1), a highly degraded seco-triterpene derivative, together with the known palbinone, has been isolated from the whole plant Paeonia suffruticosa var. papaveracea (Andr.) Kerner. The structure with absolute configuration of 1 was determined via comprehensive NMR and MS analyses, as well as NMR and ECD calculations. A plausible biosynthetic pathway for 1 was proposed. Compound 1 showed weak cytotoxicity against Hela cancer cell line with an IC₅₀ value of 26.2 μM, while palbinone exhibited a moderate inhibition on NO production with an IC₅₀ of 18.3 μM.     

Diseño automático de tableros óptimos de puentes de carretera de vigas artesa prefabricadas mediante algoritmos meméticos híbridos

This paper deals with the minimum cost automatic design of precast bridge decks made of U-beams and an upper slab. It uses a hybrid memetic algorithm that combines the population search of solutions by genetic algorithms and a search by variable neighborhood. This algorithm is applied to a bridge made of two isostatic U-beams of 20-40 m of span and a width of 12 m. This example has 40 discrete variables. The evaluation module takes into account the service and ultimate limit states usually considered for these structures, i.e. flexure, shear, torsion, cracking, deflections, etc. The use of the memetic algorithm requires its previous calibration. Each of the heuristics is run 12 times, obtaining information about the minimum and average values, as well as the scatter. The parametric study showed a good correlation for the cost, the number of strands and the steel and concrete quantities with the span length. Savings have been found between 8 and 50% compared to other structures really executed. The presented procedure allows the practical application to the real design and its adaptation to the precast process.     

Structural recovery mechanism after shear induced orientation of multiwalled carbon nanotube in polypropylene matrix

In this work the flow induced orientation and the governing mechanism of structural recovery of multi-walled carbon nanotube (MWCNT) filled polypropylene nanocomposites were investigated. A series of linear and nonlinear melt rheological measurements including stress growth and time sweep experiments were performed at different temperatures to study the structural breakdown, nanoparticles orientation, subsequent structural recovery and MWCNT loadings. The results showed that the structural recovery occurred in two stages. The first stage, initial agglomeration, showed a quick recovery which was independent of temperature, can be interpreted in terms of inter-particle van der Waals interactions. This structural recovery stage had major contribution in the storage modulus increment. The second stage of the recovery, secondary agglomeration, was slower and dependent on temperature, can be attributed to rotary diffusion of nanoparticles. This stage had minor contribution to the storage modulus increase. Storage modulus increment in both of these agglomeration was attributed to the increase of nanotube-nanotube contacts. Both of these stages were confirmed by transmission electron micrographs. These result were in a good agreement with those calculated using van der Waals and diffusion concepts.     

Computationally Efficient Changepoint Detection for a Range of Penalties

In the multiple changepoint setting, various search methods have been proposed, which involve optimizing either a constrained or penalized cost function over possible numbers and locations of changepoints using dynamic programming. Recent work in the penalized optimization setting has focused on developing an exact pruning-based approach that, under certain conditions, is linear in the number of data points. Such an approach naturally requires the specification of a penalty to avoid under/over-fitting. Work has been undertaken to identify the appropriate penalty choice for data-generating processes with known distributional form, but in many applications the model assumed for the data is not correct and these penalty choices are not always appropriate. To this end, we present a method that enables us to find the solution path for all choices of penalty values across a continuous range. This permits an evaluation of the various segmentations to identify a suitable penalty choice. The computational complexity of this approach can be linear in the number of data points and linear in the difference between the number of changepoints in the optimal segmentations for the smallest and largest penalty values. Supplementary materials for this article are available online.     

Ultrasonic-assisted synthesis of Ce doped cubic–hexagonal ZnTiO3 with highly efficient sonocatalytic activity

Ce doped ZnTiO₃ as a novel catalyst with highly efficient and stable sonocatalytic activity was synthesized via an ultrasound-assisted sol–gel method using non-ionic surfactant Pluronic F127 as structure directing agent. Synthesized samples were characterized by using various techniques, such as XRD, TEM, SEM, EDX, ​XRF, BET, DRS, and PL, and their sonocatalytic activity studied toward degradation of p-Nitrophenol as a model organic compound. The synthesized mesoporous Ce/ZnTiO₃ had mixed cubic–hexagonal phase with large surface area (118.2 m² g^–1) and narrow pore size distribution (4.9 nm). The effects of cerium concentration, calcination temperature, and calcination time on the structure and the sonocatalytic activity of Ce/ZnTiO₃ were studied in detail. XRD results were suggested that the relation between the phase structure and the catalytic activity is considerable. Significant decrease in band-gap and PL intensity was observed with increasing the cerium concentration in the ZnTiO₃. It became clear that the Ce/ZnTiO₃ (0.81 mol%) shows high sonocatalytic activity compared with pure ZnTiO₃ and other Ce/ZnTiO₃ samples as well as commercial TiO₂-P25. The possible mechanism for the enhanced sonocatalytic activity of Ce/ZnTiO₃ was discussed in details. The electrical energy consumption was also considered during sonocatalytic experiments.     

Fullerenes as mass sensors: A numerical investigation

This paper investigates the novel development of a mass sensitive nanosensor based on the use of individual spherical fullerenes. The main advantage of the mass sensing ability of spherical fullerenes in comparison with other nanomaterials such as carbon nanotubes (CNTs) or graphene nanoribbons (GNRs) is the fact that they present almost perfect geometric symmetry and thus a unique vibrational behavior which is independent from the location of the externally added nanoparticle. The study is conducted by the use of a computationally effective numerical scheme based on the adoption of appropriate three dimensional line spring elements as well as point mass elements to simulate the atomistic structure of fullerenes and interatomic interactions appearing between carbon atoms. The free vibration of C₂₀, C₆₀, C₈₀ and C₁₈₀ molecules is analyzed without and with an external nanoparticle of specific mass attached on their structure to calculate the arisen change in their natural frequencies and corresponding shape modes. A parametric study concerning the magnitude and location of the added mass is performed in order to evaluate the mass sensing ability of the fullerenes under consideration.     

A new nonlinear optical silicate carbonate K2Ca[Si2O5](CO3) with a hybrid structure of kalsilite and soda-like layered fragments

Single crystals of a new silicate carbonate, K₂Ca[Si₂O₅](CO₃), have been synthesized in a multi-components hydrothermal solution with a pH value close to neutral and a high concentration of a carbonate mineralizer. The new compound has an axial structure (s.g. P6₃22) with unit cell parameters a = 5.04789 (15), c = 17.8668 (6) Å. Pseudosymmetry of the structure corresponds to s.g. P6₃/mmc which is broken only by one oxygen position. The structure consists of two layered fragments: one of the type of the mineral kalsilite (KAlSiO₄) and the other of the high-temperature soda-like α-Na₂CO₃, Ca substituting for Na. The electro-neutral layer K₂[Si₂O₅] (denoted K) as well as the layer Ca(CO₃) (denoted S) may separately correspond to individual structures. In K₂Ca[Si₂O₅](CO₃) the S-K layers are connected together via Ca-O interactions between Ca atoms from the carbonate layer and apical O atoms from the silicate one, and also via K-O interlayer interactions. A hypothetical acentric structure, sp.gr. P-62c, is predicted on the basis of the order-disorder theory. It presents another symmetrical option for the arrangement of K-layers relative to S-layers. The K,Ca-silicate-carbonate powder produces a moderate SHG signal that is two times larger that of the α-quartz powder standard and close to other silicates with acentric structures and low electronic polarizability.     

Evaluation of SARs for the prediction of skin irritation/corrosion potential–structural inclusion rules in the BfR decision support system†

The German Federal Institute for Risk Assessment (BfR) has developed a Decision Support System (DSS) to assess certain hazardous properties of pure chemicals, including skin and eye irritation/corrosion. The BfR–DSS is a rule-based system that could be used for the regulatory classification of chemicals in the European Union. The system is based on the combined use of two predictive approaches: exclusion rules based on physicochemical cut-off values to identify chemicals that do not exhibit a certain hazard (e.g., skin irritation/corrosion), and inclusion rules based on structural alerts to identify chemicals that do show a particular toxic potential. The aim of the present study was to evaluate the structural inclusion rules implemented in the BfR–DSS for the prediction of skin irritation and corrosion. The following assessments were performed: (a) a confirmation of the structural rules by rederiving them from the original training set (1358 substances), and (b) an external validation by using a test set of 200 chemicals not used in the derivation of the rules. It was found as a result that the test data set did not match the training set relative to the inclusion of structural alerts associated with skin irritation/corrosion, albeit some skin irritants were in the test set.     

钙钛矿型氧化物负载纳米金属催化剂结构的动态调变及其催化氧化CO反应性能

研究了钛酸钡和钛酸钙担载的Ag和Pt纳米催化剂的表面结构随氧化-还原处理过程的动态变化及其对CO完全氧化反应性能的影响.发现氧化物担载的Ag催化剂在氧化处理后其催化活性较还原处理的高; X射线衍射(XRD)和X射线光电子能谱(XPS)表征结果表明,氧化处理能够提高载体表面Ag颗粒的分散度,而还原处理导致Ag颗粒的聚集,从而降低了催化氧化CO反应的活性.氧化-还原处理改变了担载Ag纳米粒子的尺寸并影响其CO氧化反应活性.与此相反,氧化物担载的Pt催化剂在还原处理后所表现出的CO氧化反应活性较氧化处理的高; 对比研究发现,氧化和还原处理后Pt纳米粒子的尺寸基本相同,但是氧化处理的样品中Pt表面物种以氧化态为主,而还原处理后Pt表面物种主要为金属态.Pt纳米粒子表面化学状态随氧化-还原处理的调变是导致表面催化活性差异的主要原因.     

Lipase mediated separation of triterpene structural isomers, α- and β-amyrin

Pentacyclic triterpenoids α- and β-amyrin possess a wide range of biological and pharmacological activities. High structural similarity between these two structural isomers makes their chromatographic separation an ineffective and tedious choice. In this study, Candida rugosa lipase catalyzed separation protocol for the isolation of individual isomers has been developed. In the presence of vinyl acetate as the acyl donor, Candida rugosa lipase carried out acetylation of β-amyrin more efficiently as compared to α-amyrin leading to a kinetic separation. The conditions of transesterification reaction were optimized systematically, which was utilized to separate α- and β-amyrin from a mixture obtained from the latex of Plumeria obtusa.