Inverse Hall–Petch like behaviour in a mechanically milled nanocrystalline Al5Fe2 intermetallic phase

In the present investigation, the indentation study on the high-energy ball-milled nanocrystalline Al₅Fe₂ intermetallic compound has established the inverse Hall–Petch (IHP) behaviour. The structural characterisation of the milled powder particles by X-ray diffraction (XRD) and transmission electron microscopy has shown the evolution of nanocrystalline phase. Micro-indentation measurements have revealed the increase in hardness with decreasing grain size, reaching to a maximum of 9.0 ± 0.3 GPa up to a grain size of 32 ± 4 nm, followed by a decrease. The decrease in hardness with further refinement, an indication of grain size softening, demonstrates the IHP-like behaviour. The deviation from the Hall–Petch behaviour has been discussed using various models based on the dislocations and grain boundary-mediated processes. From the analysis, it appears that the model based on mesocopic grain boundary sliding phenomena is more appropriate to account for the observed grain size softening.     

Ca2+ and cAMP regulations of microtubule sliding in hyperactivated motility of bull spermatozoa

To reach and fertilize the egg, mammalian spermatozoa change their flagellar movement in the female reproductive tract, named hyperactivation. The biochemical analyses of the hyperactivated movement using demembranated spermatozoa defined the factors inducing this peculiar movement; namely, large asymmetrical flagellar movement observed in the early stage of the hyperactivation was induced with a high Ca²⁺ concentration while large symmetrical flagellar movement in the late stage of the hyperactivation was generated with low Ca²⁺ and high cAMP concentrations. Under these conditions, the microtubule sliding of bull sperm flagella was investigated by disintegrating the sperm flagella with MgATP²⁻ after extracting their plasma membrane and mitochondria. The large asymmetrical flagellar movement was caused by a long sliding displacement of a fiber of the doublet microtubules. On the other hand, the large symmetrical flagellar movement was generated by a large amount of microtubule sliding by many doublet microtubules.     

Electro-Mechanochemical Atom Transfer Radical Cyclizations using Piezoelectric BaTiO3

The formation and regeneration of active Cu^I species is a fundamental mechanistic step in copper-catalyzed atom transfer radical cyclizations (ATRC). Typically, the presence of the catalytically active Cu^I species in the reaction mixture is secured by using high Cu^I catalyst loadings or the addition of complementary reducing agents. In this study it is demonstrated how the piezoelectric properties of barium titanate (BaTiO₃) can be harnessed by mechanical ball milling to induce electrical polarization in the strained piezomaterial. This strategy enables the conversion of mechanical energy into electrical energy, leading to the reduction of a Cu^II precatalyst into the active Cu^I species in copper-catalyzed mechanochemical solvent-free ATRC reactions.     

Mechanochemistry in Portugal—A Step towards Sustainable Chemical Synthesis

In Portugal, publications with mechanochemical methods date back to 2009, with the report on mechanochemical strategies for the synthesis of metallopharmaceuticals. Since then, mechanochemical applications have grown in Portugal, spanning several fields, mainly crystal engineering and supramolecular chemistry, catalysis, and organic and inorganic chemistry. The area with the most increased development is the synthesis of multicomponent crystal forms, with several groups synthesizing solvates, salts, and cocrystals in which the main objective was to improve physical properties of the active pharmaceutical ingredients. Recently, non-crystalline materials, such as ionic liquids and amorphous solid dispersions, have also been studied using mechanochemical methods. An area that is in expansion is the use of mechanochemical synthesis of bioinspired metal-organic frameworks with an emphasis in antibiotic coordination frameworks. The use of mechanochemistry for catalysis and organic and inorganic synthesis has also grown due to the synthetic advantages, ease of synthesis, scalability, sustainability, and, in the majority of cases, the superior properties of the synthesized materials. It can be easily concluded that mechanochemistry is expanding in Portugal in diverse research areas.     

Green Strategies for the Preparation of Enantiomeric 5–8-Membered Carbocyclic β-Amino Acid Derivatives through CALB-Catalyzed Hydrolysis

Candida antarctica lipase B-catalyzed hydrolysis of carbocyclic 5–8-membered cis β-amino esters was carried out in green organic media, under solvent-free and ball-milling conditions. In accordance with the high enantioselectivity factor (E > 200) observed in organic media, the preparative-scale resolutions of β-amino esters were performed in tBuOMe at 65 °C. The unreacted β-amino ester enantiomers (1R,2S) and product β-amino acid enantiomers (1S,2R) were obtained with modest to excellent enantiomeric excess (ee) values (ee_s > 62% and ee_p > 96%) and in good chemical yields (>25%) in one or two steps. The enantiomers were easily separated by organic solvent/H₂O extraction.     

Simultaneous Brownian motion of N particles in a temperature gradient

A system of N Brownian particles suspended in a nonuniform heat bath is treated as a thermodynamic system with internal degrees of freedom, in this case their velocities and coordinates. Applying the scheme of nonequilibrium thermodynamics, one then easily obtains the Fokker-Planck equation for simultaneous Brownian motion of N particles in a temperature gradient. This equation accounts for couplings in the motion as a result of hydrodynamic interactions between particles.     

高能机械球磨法制备V-Ti-O超细微粒催化剂

负载型V2O5/TiO2氧化物催化剂因具有优良的催化性能而广泛地用于烃类选择性氧化[1,2]和氮氧化物选择性催化还原(SCR)[3]. 迄今,所研究的负载型V2O5/TiO2氧化物催化剂大多是采用浸渍法制备的[2,4～6],通过调整催化剂的组成[2,5]、引入适当的助剂组分[2,6]和选择适宜的反应操作条件[2,5]可进一步优化其催化性能.     

A kind of carbon whiskers in new structure and morphology

Carbon whiskers with new structure and morphology were observed when heating the milled graphite. Transmission electron microscopy (TEM) and high resolution electron microscopy (HREM) show that carbon layers are almost perpendicular to the growth axes of carbon whiskers. Field emission scanning electron microscopy (FESEM) indicates that there are spirals appearing on the surface of the whiskers. The structure analysis shows that the growth mechanism of carbon whiskers is related to the trace amount of ZrC in the heated samples.     

Synergetic catalytic effect of rGO,Pd, Fe3O4 and PPy as a magnetically separable and recyclable nanocomposite for coupling reactions in green media

In this paper, rGO/Pd–Fe₃O₄@PPy as an efficient stable nanocomposite was synthesized. To understand the synergetic effects of rGO, Pd, Fe₃O₄ and PolyPyrrole, the performance of rGO/Pd–Fe₃O₄@PPy as a heterogeneous recyclable nanocatalyst in the green synthesis of C‐C and C‐O coupling products, as well as different conditions are studied. Synthesized rGO/Pd–Fe₃O₄@PPy was characterized by FT‐IR, XRD, FE‐SEM, EDS, TGA and AFM analysis. Best results are obtained under sonication in H₂O for C‐C coupling and by ball‐milling for C‐O coupling. The benefits of this method include: green solvents and conditions, absence of external base, low reaction times with high yield and easy work‐up method.