Computer-aided molecular design of alternative solvents based on phase equilibrium synergism in mixtures

A systematic methodology is proposed that finds binary azeotropic mixtures as new alternative solvents for the extraction process of volatile aroma molecules widely used in perfume and cosmetic industries. We investigated the use of the reverse engineering approach with Computer Aided Product Design (CAPD) instead of the traditional ‘trial and error’ approach. First, the design problem is defined from the real functionalities of the classical solvents. They are translated into physicochemical properties and the bound values for each property are defined. The reverse engineering method coupled to CAPD consists in using optimization techniques for building molecular structures that match as best as possible the complete set of target physicochemical properties, thus defining for each candidate a performance index. Property values are evaluated by using group contribution methods of each molecular structure generated by CAPD tool or by using database values. Acknowledging the contradictory relationship between two selected physicochemical properties i.e, low boiling temperature and high flash point which is rarely found in pure components, binary azeotropic mixtures were studied in order to enhance the global performance of solvent candidates. Dimethyl carbonate (DMC) is an existing solvent for the extraction of odorous molecules from plants that exhibits a good ratio between the boiling temperature and the flash point. It is selected as the key component for designing binary azeotropic mixtures. DMC. The global performance of the binary azeotropic mixtures was verified by means of calculations of the vapour-liquid equilibrium and liquid – liquid equilibrium using Modified UNIFAC method as thermodynamic method

Observation of the algebraic localization-delocalization transition in a 1D disordered potential with a bias force

In a one-dimensional (1D) disordered potential, quantum interferences leading to Anderson lo-calization are ubiquitous, such that all wave-functions are exponentially localized. Moreover, no phase transition toward delocalization is expected in 1D. This behavior is strongly modified in the presence of a bias force. We experimentally study this case, launching a non-interacting 39 K Bose-Einstein condensate in a 1D disordered potential induced by a far-off-resonance laser speckle, while controlling a bias force. In agreement with theoretical predictions, we observe a transition between algebraic localization and delocalization as a function of our control parameter that is the relative strength of the disorder against the bias force. We also demonstrate that the initial velocity of the wave-packet only plays a role through an effective disorder strength due to the correlation of the disorder. Adding a bias force is a quite natural way to probe the transport properties of quantum systems, a subject of broad interest that can be in particular addressed with atomic quantum gases thanks to their high degree of control and versatility [1]. For example, Bloch oscillations has been measured through the addition of a constant force to atoms in periodic potential induced by an optical lattice [2]. A force applied to a harmonic trap is equivalent to a trap displacement. The response to such a displacement permits to reveal the fluid or insulating behavior of atomic systems. In 1D interacting Bose gases, the pinning transition by an optical lattice [3] or the insulating transition in quasi-disordered optical lattice [4, 5] have been studied in this manner. More recently, transport in quantum gases is also studied in junction-type setup more analogous to condensed-matter systems: two reservoirs with different chemical potentials are connected through a constriction. For example, in a gas of fermions, the quantization of conductance through a quantum point contact [6] and the superfluid to normal transition in a disordered thin film have been observed [7]. In our work, we focus on the transport of non-interacting particles in disordered media. Without a bias force, quantum interferences between multiple paths lead to Anderson localization [8] whose signature is an exponential decay in space of single particle wave-function [9]. This phenomenon is ubiquitous in wave/quantum physics and it has been observed in many physical contexts [10] including condensed-matter [11] and ultra-cold atoms [12-14]. One-dimensional truly disordered systems are always localized [15], contrary to the 3D case where a phase transition between localized and extended single particle wave-functions takes place as a function of the disorder strength [16-18]. The localization properties of 1D disordered systems are modified in the presence of a bias force. Theoretical studies predict a transition from algebraic localization to delocalization as a function of a single control non-dimensional parameter α which is the ratio of the force to the disorder strength [19, 20]. Physically, α is the relative energy gain ∆E/E of a particle of energy E when moving over a localization length. Interestingly, in a 1D white noise disorder, this quantity is independent of E as the localization length is proportional to E. If α is small, the force does not considerably change the localization behavior of the particle while for large α its dynamics is severely affected leading to delocalization. This localization-delocalization transition is predicted in the infinite time limit for white noise disorder [20]. In a correlated disorder, as the one produced from a far-off-resonance laser speckle [21], the situation is more complicated. Speckles have no Fourier component beyond a spatial frequency 2k c. As a consequence, back-scattering and localization are not expected in the framework of Born approximation for atoms with wavevectors k > k c [12, 22]. Since localized wave-functions always have a small fraction at long distance corresponding to large energies and momenta in the presence of a bias force, we thus expect correlation-induced delocalization at infinite time. However, signatures of the algebraic localization-delocalization transition are predicted to be observable at transient times [20]. In this paper, we report on the observation of the algebraic localization-delocalization transition with cold-atoms propagating in a one dimensional disordered potential in the presence of a controlled bias force. We experimentally show that the non-dimensional parameter α is the only relevant parameter to describe the transition. We notice that the initial velocity of the quantum wave packet only plays a role through the correlation of the disordered potential, showing that the transition is in-trinsically energy independent. In the localized regime, we demonstrate an algebraic decay of the density and measure the corresponding decay exponent as a function of α. At large disorder strength, a saturation of the exp

Relation between magnetization and Faraday angles produced by ultrafast spin-flip processes within the three-level A-type system

Ultrafast magneto-optical (MO) experiments constitute a powerful tool to explore the magnetization dynamics of diverse materials. Over the last decade, there have been many theoretical and experimental developments on this subject. However, the relation between the magnetization dynamics and the transient MO response still remains unclear. In this work, we calculate the magnetization of a material, as well as the magneto-optical rotation and ellipticity angles measured in a single-beam experiment. Then, we compare the magnetization to the MO response. The magnetic material is modeled by a three-level A-type system, which represents a simple model to describe MO effects induced by an ultrafast laser pulse. Our calculations use the density matrix formalism, while the dynamics of the system is obtained by solving the Lindblad equation taking into account population relaxation and dephasing processes. Furthermore, we consider the Faraday rotation of the optical waves that simultaneously causes spin-flip. We show that the Faraday angles remain proportional to the magnetization only if the system has reached the equilibrium-state, and that this proportionality is directly related to the population and coherence decay rates. For the non-equilibrium situation, the previous proportionality relation is no longer valid. We show that our model is able to interpret some recent experimental results obtained in a single-pulse experiment. We further show that, after a critical pulse duration, the decrease of the ellipticity as a function of the absorbed energy is a characteristic of the system

Extraction and characterization of cellulosic nanowhisker obtained from discarded cotton fibers

This study aimed to characterize cellulose nanowhiskers extracted from discarded cotton fibers. The nanocellulose was characterized by dynamic light scattering, zeta potential, Scanning Transmission Electron Microscopy (STEM), Atomic force microscopy (AFM) and X-ray powder diffraction (XRD). The nanocrystals are characterized by a rod-like morphology with sizes between 100 nm and 300 nm. The acidic hydrolyses applied to the extract nanocrystals increased the crystallinity index from 72 to 86%. The average length and diameter obtained were 98.1±4.7 and 8.0±3.4 nm, respectively. The aspect ratio of the fibers, around 12.3, was lower than the values usually reported in the literature. The dynamic light scattering results were in accordance with the nano crystal dimensions showing an average size of 235 nm. Cellulose nanowhiskers obtained from cotton rejected by textile industry due to their abundance, low cost, high crystallinity, strength, low weight and biodegradability, are the ideal candidates for the processing of polymer nanocomposites.(undefined

Modelling and experimental validation of dimethyl carbonate solvent recovery from an aroma mixture by batch distillation

Modelling and experimental validation of solvent recovery from an aroma mixture by batch distillation process is presented, with particular emphasis of the effect of the prediction of the physicochemical properties and the phase equilibrium data on the content of the aroma compounds in the distillate cuts. The illustrative case study refers to an industrial batch distillation to recover dimethyl carbonate (DMC) from an extract generated by a solvent extraction process involving variable natural raw materials for tailored perfume and fragrance applications. Due to the high number of aroma compounds in natural extracts, a synthetic mixture containing six target aroma compounds (α-pinene, eucalyptol, linalool, cis-3-hexenol, fenchone and benzyl acetate) was mixed with DMC for the modelling and experimental studies of the batch distillation process. The methodology is tested through the simulation of the process with BatchColumn® software. As physicochemical properties of the aroma compounds and the vapour–liquid equilibrium (VLE) of all involved mixtures are required for simulation study, group contribution methods are used to predict missing properties such as vapour pressure, vaporisation enthalpy and liquid and vapour heat capacities. For VLE calculation, the modified UNIFAC group contribution method is considered and new binary interaction parameters for the main groups COO and CH2O are regressed from experimental data. Simulation results are in good agreement with experiments carried out in a fully automated batch distillation column at 15 kPa and help optimise the industrial process operation. The proposed methodology can be applied for the design of other solvent recovery process in fragrance industry

Surface properties of distinct nanofibrillated celluloses assessed by inverse gas chromatography

The adhesion and surface properties of nanocelluloses are an important issue to consider when using this material for composites production, in food packaging or coatings, as well as for determining the influence of added functional groups. In the present work, the surface properties of two nanofibrillated celluloses obtained by mild 2,2,6,6-tetramethylpiperidine-1- oxyl radical (TEMPO)-mediated oxidation with distinct mechanical treatment intensity in a homogenizer (5 and 15 passes), and one nanofibrillated cellulose obtained by enzymatic process, were thoroughly assessed by inverse chromatography, at infinite dilution conditions. The dispersion component of the surface energy ( s d) was 42-46 mJ m-2 at 40 ºC for the TEMPO nanofibres and 52 mJ m-2 for the enzymatic nanocellulose. It was confirmed, based on the determination of the specific components of the works of adhesion and enthalpies of adsorption with polar probes, that the surfaces of the materials have a more Lewis acidic than Lewis basic character. Regarding TEMPO nanofibres, a slight increase of Lewis acidity/basicity ratio seemed to occur for the more nanofibrillated material (15-passes). Higher specific interactions with polar probes were found for enzymatic nanocellulose. The higher values of s d and specific interactions observed for the enzymatic nanocellulose could partly be due to the higher crystallinity of this sample. On the other hand, the increase of the acidity/basicity ratio (as well as of the s d value) for the 15-passes vs. 5-passes TEMPO nanofibres was attributed to a higher exposition of the hydroxyl groups of cellulose at the surface of the former material

Diagnostic criteria for constitutional mismatch repair deficiency syndrome: suggestions of the European consortium 'care for CMMRD' (C4CMMRD)

Constitutional mismatch repair deficiency (CMMRD) syndrome is a distinct childhood cancer predisposition syndrome that results from biallelic germline mutations in one of the four MMR genes, MLH1, MSH2, MSH6 or PMS2. The tumour spectrum is very broad, including mainly haematological, brain and intestinal tract tumours. Patients show a variety of non-malignant features that are indicative of CMMRD. However, currently no criteria that should entail diagnostic evaluation of CMMRD exist. We present a three-point scoring system for the suspected diagnosis CMMRD in a paediatric/young adult cancer patient. Tumours highly specific for CMMRD syndrome are assigned three points, malignancies overrepresented in CMMRD two points and all other malignancies one point. According to their specificity for CMMRD and their frequency in the general population, additional features are weighted with 1-2 points. They include multiple hyperpigmented and hypopigmented skin areas, brain malformations, pilomatricomas, a second childhood malignancy, a Lynch syndrome (LS)-associated tumour in a relative and parental consanguinity. According to the scoring system, CMMRD should be suspected in any cancer patient who reaches a minimum of three points by adding the points of the malignancy and the additional features. The diagnostic steps to confirm or refute the suspected diagnosis are outlined. We expect that application of the suggested strategy for CMMRD diagnosis will increase the number of patients being identified at the time when they develop their first tumour. This will allow adjustment of the treatment modalities, offering surveillance strategies for second malignancies and appropriate counselling of the entire family