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Partial oxidation of allylic and primary alcohols with $O_2$ by photoexcited $TiO_2$
Molinari, Alessandra,Montoncello, Marco,Rezala, Houria,Maldotti, Andrea Korean Society of Photoscience 2009 Photochemical & photobiological sciences Vol.8 No.5
Proper reaction conditions have been found for the conversion of geraniol, citronellol, trans-2-penten-1-ol and 1-pentanol to the corresponding aldehydes with good chemo-selectivity (>70%) by photochemical excitation of suspensions of P25-$TiO_2$. It is demonstrated that adsorption of the alcohol on the surface as an alcoholate is necessary for its oxidation. ESR-spin trapping experiments point out that oxidation of alcohols starts with the formation of alkoxide radicals. Water content in the dispersing medium strongly inhibits alcohol adsorption and subsequent oxidation. In fact, water increases the polarity of the dispersing medium favouring the affinity between the polar alcohol and the $CH_3CN-H_2O$ mixture itself; moreover, water competitive adsorption with the alcohol causes the removal of the latter from the photocatalytic surface with consequent difficult oxidation, as evidenced by ESR-spin trapping investigation. The reactivity of the alcohol on the surface of photoexcited P25-$TiO_2$ is also affected by the nature of its hydrophobic aliphatic chain: geraniol and citronellol are more susceptible to the water content than their short analogues trans-2-penten-1-ol and 1-pentanol. Moreover, in anhydrous $CH_3CN$, specific interaction between the surface and the OH group enhances the reactivity of the primary aliphatic alcohols towards their partial oxidation to aldehyde, which can be accumulated in the reaction environment.
Madureira Alana,Molinari Mayla D. C.,Marin Silvana R. R.,Pagliarini Renata Fuganti,Henning Fernando A.,Nepomuceno Alexandre L.,Finatto Taciane,Mertz-Henning Liliane M. 한국작물학회 2023 Journal of crop science and biotechnology Vol.26 No.4
The present study aimed to identify the relationship between lignin content in soybean pods, pod dehiscence rate, gene expression from phenylpropanoid pathway, cell wall lignifcation, and deterioration of seed due to weather. To evaluate the weathering deterioration, an experiment simulating 150 mm of rainfall was performed in greenhouse conditions. Gene expression was assessed by RT-qPCR. Results showed that soybean cultivars BRS Jiripoca and BRS 388 RR considered tolerant to weathering deterioration, presented higher levels of lignin content in pods. The data showed that dehiscence rate was neither a trait involved in weathering deterioration tolerance nor in lignin content in soybean pods. Lignin content and weathering deterioration were highly negatively correlated, probably due to changes in cell wall permeability to water accordingly to lignin level. Higher expression levels of genes involved in lignin biosynthesis and cell wall lignifcation were identifed in both tolerant cultivars, however, with opposite expression profles and in diferent developmental phases, suggesting a possible temporal strategy to cope with environmental adverse conditions.
Hardenability of Low Alloy Sintered Mn Steels
Zendrona Marianna,Molinari Alberto,Girardini Luca 한국분말야금학회 2006 한국분말야금학회 학술대회논문집 Vol.2006 No.1
Manganese is an alloying element that improves the hardenability of steels. It could be a valid substitute in sintered steels, increasing mechanical properties. The hardenability of three low alloy Mn steels was studied to establish the influence of manganese on the heat treatments. The Grossmann approach was adopted, which uses cylinders with different diameters to induce different gradients of cooling rate in the cross section. The correlation of microstructure and microhardness to the actual cooling rate makes the results independent on the process parameters and applicable to each industrial condition, once the actual cooling rate in the parts is known.
Solvency II – Considering Risk Dependencies
Tristan Nguyen,Robert Danilo Molinari 한국리스크관리학회 2010 리스크 管理硏究 Vol.21 No.1
In November 2009 the European Parliament adopted a directive "on the taking-up and pursuit of the business of Insurance and Reinsurance" (SolvencyII). According to this SolvencyII directive the Solvency Capital Requirement (SCR) corresponds to the economic capital needed to limit the probability of ruin to 0.5This implies that (re-)insurance undertakings will have to identify their overall loss distributions. The standard approach of the mentioned SolvencyII directive proposes the use of a correlation matrix for the aggregation of the single so-called risk modules respectively sub-modules. In our paper we will analyze the method of risk aggregation via the proposed application of correlations. We will find serious weaknesses, particularly concerning the recognition of extreme events, e.g. natural disasters, terrorist attacks etc. The reason for this is that correlations compress information about dependencies into a single ratio. Therefore important information concerning the tail of a distribution may possibly not be considered. In contrast, multivariate distribution functions provide full information with respect to dependencies between the relevant risks. However, aggregation of risks through "traditional"multivariate modeling causes technical difficulties. A possible solution for this dilemma can be seen in the application of copulas. We come to the conclusion that it would have been desirable to fix the concept of copulas in the new solvency directive. Even though the concept of copulas is not explicitly mentioned in the directive, there is still a possibility of applying it. (Re-)insurers will be able to design their internal models by using an aggregation method more complex but even more precisely (e.copulas) than the solely utilization of a correlation matrix. It is clear that modeling dependencies with copulas would incur significant costs for smaller companies that might outbalance the resulting more precise picture of the risk situation of the insurer. However, incentives for those companies who use copulas, e.reduced solvency capital requirements compared to those who do not use it, could push the deployment of copulas in risk modeling in general.
Design for Powder Metallurgy - Predicting Anisotropic Dimensional Change on Sintering of Real Parts
I. Cristofolini,A. Molinari,M. Zago,S. Amirabdollahian,O. Coube,M. J. Dougan,M. Larsson,M. Schneider,P. Valler,J. Voglhuber,L. Wimbert 한국정밀공학회 2019 International Journal of Precision Engineering and Vol.20 No.4
Anisotropic dimensional change on sintering may strongly affect the precision of parts produced by press and sinter. In previous work a design procedure accounting for anisotropic dimensional change of axi-symmetric parts (disks and rings) has been developed on the basis of experimental data. In this work the procedure has been applied to predict the anisotropic dimensional change of real parts produced in industrial conditions, providing that coaxial rings were identified in the geometry of the actual parts. Parts were highly different for material, complexity of geometry, green density and process conditions. Parts were measured in the green and sintered state and the measured dimensional changes were compared to the predicted ones, finding a good agreement. The procedure was also adapted to predict dimensional change of an oval feature, and highly satisfactory results were obtained.
A NOTE ON CONCIRCULAR STRUCTURE SPACE-TIMES
Mantica, Carlo Alberto,Molinari, Luca Guido Korean Mathematical Society 2019 대한수학회논문집 Vol.34 No.2
In this note we show that Lorentzian Concircular Structure manifolds $(LCS)_n$ coincide with Generalized Robertson-Walker space-times.
Microstructure and Mechanical Properties of Nanostructured Aluminum Consolidated by SPS
Zadra Mario,Casari Francesco,Molinari Alberto 한국분말야금학회 2006 한국분말야금학회 학술대회논문집 Vol.2006 No.1
Nanostructured aluminum powders were obtained by means of planetary ball milling with methanol as the Process Control Agent (PCA). The behavior, during milling, was considered measuring the microhardness and grain size at different milling times. Bulk near-full density samples were sintered using the Spark Plasma Sintering technology with different schedules: temperature of and , pressure of 30 MPa and 60 MPa and different modes of applying the pressure were changed in order to understand the behavior during sintering. All the samples retained their nanostructure with an increase of the grain size from about 46 up to 70-90 nm.
Ilaria Cristofolini,Nicolò Corsentino,Alberto Molinari,Mats Larsson 한국정밀공학회 2014 International Journal of Precision Engineering and Vol. No.
In the conventional press and sinter process, dimensional change on sintering determines the precision of the final parts, providingthat a good dimensional precision of green parts is ensured. Anisotropic dimensional change on sintering may be detrimental to theprecision of Powder Metallurgy (PM) parts, and it should be considered in the design step. The effect of material and geometry onthe anisotropic dimensional change is studied in this work. Four different iron alloys and five different geometries were considered. Dimensions were measured both on green and on sintered parts and the anisotropy of dimensional change was evaluated andcorrelated to the material and geometry. The effect of neglecting anisotropy in the design step was investigated, in terms ofdimensional tolerances, which can be obtained with different process capabilities. A model to describe the effect of material andgeometry on the anisotropic dimensional change is also being developed.