Application of off-line pyrolysis with dynamic solid-phase microextraction to the GC–MS analysis of biomass pyrolysis products

Pyrolysis coupled with dynamic solid-phase micro extraction (Py-SPME) followed by GC–MS analysis was applied to the determination of volatile compounds evolved by a micro-scale off-line pyrolysis apparatus, in order to extend the information affordable with this type of analytical equipment. The Py-SPME method with a carboxen/PDMS fiber working in the retracted mode was tested on four biomass samples (switchgrass, sweet sorghum, corn stalk and poplar) for qualitative analysis of semi-volatile pyrolysis products and quantitative determination of main volatiles (C₁–C₄) pyrolysis products. The developed procedure allowed capturing and analysis of all GC analyzable compounds, without memory effects and with good peak resolution also for early GC-eluting compounds. Twelve main volatile pyrolysis products, including hydroxyacetaldehyde and acetic acid, were successfully quantified; in spite of the intrinsic variability introduced by dynamic SPME sampling, results were relatively accurate and consistent with literature data on bench pyrolysis reactors.     

Characterization of Basil Volatile Fraction and Study of Its Agronomic Variation by ASCA

Basil is a plant known worldwide for its culinary and health attributes. It counts more than a hundred and fifty species and many more chemo-types due to its easy cross-breeds. Each species and each chemo-type have a typical aroma pattern and selecting the proper one is crucial for the food industry. Twelve basil varieties have been studied over three years (2018–2020), as have four different cuts. To characterize the aroma profile, nine typical basil flavour molecules have been selected using a gas chromatography–mass spectrometry coupled with an olfactometer (GC–MS/O). The concentrations of the nine selected molecules were measured by an ultra-fast CG e-nose and Principal Component Analysis (PCA) was applied to detect possible differences among the samples. The PCA results highlighted differences between harvesting years, mainly for 2018, whereas no observable clusters were found concerning varieties and cuts, probably due to the combined effects of the investigated factors. For this reason, the ANOVA Simultaneous Component Analysis (ASCA) methodology was applied on a balanced a posteriori designed dataset. All the considered factors and interactions were statistically significant (p < 0.05) in explaining differences between the basil aroma profiles, with more relevant effects of variety and year.     

Formation of Quaternary Stereogenic Centers by NHC–Cu‐Catalyzed Asymmetric Conjugate Addition Reactions with Grignard Reagents on Polyconjugated Cyclic Enones

The copper‐catalyzed conjugate addition of various Grignard reagents to polyconjugated enones (dienone and enynone derivatives) is reported. The catalyst system, composed of copper triflate and an NHC ligand, led to the unusual selective formation of the 1,4‐addition products. This reaction allows for the creation of all‐carbon chiral quaternary centers with enantiomeric excesses up to 99 %. The remaining unsaturation on the 1,4 adducts give access to valuable synthetic transformations.     

"Supramolecular" assembly of gold nanorods end-terminated with polymer "pom-poms": effect of pom-pom structure on the association modes

We report a predefined self-organization of gold nanorods (NRs) end-terminated with multiple polymer arms ("pom-poms") in higher-order structures. The assembly of polymer-tethered NRs was controlled by changing the structure of the polymer pom-poms. We show that the variation in the molecular weight of the polymer molecules and their relative location with respect to the long side of the NRs resulted in two competing association modes of the nanorods, that is, their side-by-side and end-to-end assembly, and produced bundles, chains, rings, and bundled chains of the NRs. The superposition of the two variables controlling the organization of NRs allowed us to create a map showing the variation in the longitudinal plasmonic bands of the NRs achieved by their self-assembly.     

Elliptic integral solutions of spatial elastica of a thin straight rod bent under concentrated terminal forces

In this article, we solve in closed form a system of nonlinear differential equations modelling the elastica in space of a thin, flexible, straight rod, loaded by a constant thrust at its free end. Common linearizations of strength of materials are of course not applicable any way, because we analyze great deformations, even if not so large to go off the linear elasticity range. By passing to cylindrical coordinates ρ, θ, z, we earn a more tractable differential system evaluating ρ as elliptic function of polar anomaly θ and also providing z through elliptic integrals of I and III kind. Deformed rod’s centerline is then completely described under both tensile or compressive load. Finally, the planar case comes out as a degeneracy, where the Bernoulli lemniscatic integral appears.     

A lower bound estimate of the critical load for compressible elastic solids

We determine lower bound estimates for the critical load for hyperelastic solids under monotonic dead load processes. By considering the Hadamard criterion of infinitesimal stability, we first determine a lower bound for the Hadamard stability functional; then, we develop a procedure for optimal lower bound estimates for the critical load. As examples, we apply our procedure to generalized Blatz-Ko solids under simple extension, simple compression and rectilinear shear, and compare our results with other proposals contained in the literature.     

Coherent Structures Formation During Wake-Boundary Layer Interaction on a LP Turbine Blade

Particle Image Velocimetry (PIV) measurements have been analyzed in order to characterize the dynamics of coherent structures (eddies and streaks) within the suction side boundary layer of a low pressure turbine cascade perturbed by impinging wakes. To this end, the instantaneous flow fields at low Reynolds number and elevated free-stream turbulence intensity level (simulating the real condition of the blade row within the engine) were investigated in two orthogonal planes (a blade-to-blade and a wall-parallel plane). Proper Orthogonal Decomposition (POD) has been employed to filter the instantaneous flow maps allowing a better visualization of the structures involved in the transition process of the boundary layer. For the unsteady case properly selected POD modes have been also used to sort the instantaneous PIV images in the wake passage period. This procedure allows computing phase-averaged data and visualizing structures size and intensity in the different parts of the boundary layer during the different wake passage phases. The contributions to the whole shear stress due to the largest spanwise oriented scales at the leading and trailing boundaries of the wake-jet structures and those associated with streaky structures observed in the bulk of the wake are discussed. Instantaneous images in the wall-parallel plane are filtered with POD and they allow us to further highlight the occurrence of low and high speed traveling streaks (Klebanoff mode). The periodic advection along the suction side of the high turbulent content regions carried by the wakes anticipates both formation and sinuous instability of the streaks inside the boundary layer as compared with the steady case. The dynamics driving the breakdown of the streaks and the consequent formation of nuclei with high wall-normal vorticity have been found to be almost the same in the steady and the unsteady cases. Auto-correlation of the instantaneous images are also presented in order to highlight analogies and differences in the size and spacing of streaks in the two cases. These results are also compared with the available literature concerning simplified geometries (i.e flat plate) operating under steady inflow.