Ketone–Alcohol Hydrogen‐Transfer Equilibria: Is the Biooxidation of Halohydrins Blocked?

To ensure the quasi‐irreversibility of the oxidation of alcohols coupled with the reduction of ketones in a hydrogen‐transfer (HT) fashion, stoichiometric amounts of α‐halo carbonyl compounds have been employed as hydrogen acceptors. The reason that these substrates lead to quasi‐quantitative conversions has been tacitly attributed to both thermodynamic and kinetic effects. To provide a clear rationale for this behavior, we investigate herein the redox equilibrium of a selected series of ketones and 2‐propanol by undertaking a study that combines experimental and theoretical approaches. First, the activity of the (R)‐specific alcohol dehydrogenase from Lactobacillus brevis (LBADH) with these substrates was studied. The docking of acetophenone/(R)‐1‐phenyethanol and α‐chloroacetophenone/(S)‐2‐chloro‐1‐phenylethanol in the active site of the enzyme confirms that there seems to be no structural reason for the lack of reactivity of halohydrins. This assumption is confirmed by the fact that the corresponding aluminum‐catalyzed Meerwein–Ponndorf–Verley–Oppenauer (MPVO) reactions afford similar conversions to those obtained with LBADH, showing that the observed reactivity is independent of the catalyst employed. While the initial rates of the enzymatic reductions and the IR ν(C?O) values contradict the general belief that electron‐withdrawing groups increase the electrophilicity of the carbonyl group, the calculated ΔG values of the isodesmic redox transformations of these series of ketones/alcohols with 2‐propanol/acetone support the thermodynamic control of the reaction. As a result, a general method to predict the degree of conversion obtained in the HT‐reduction process of a given ketone based on the IR absorption band of the carbonyl group is proposed, and a strategy to achieve the HT oxidation of halohydrins is also shown.     

An ATR-FTIR study of different phosphonic acids adsorbed onto boehmite

An ATR-FTIR study of the vibrational spectra of N,N-bis(2-hydroxyethyl) aminomethylphosphonic acid (BHAMP), 1-hydroxyethane-1,1′-diphosphonic acid (HEDP) and nitrilotris(methylenephosphonic acid) (NTMP) adsorbed onto boehmite is presented. The study was performed in the pH range from 5 to 9, and bands assignments are given in the 1200–900 cm^?1 wavenumber range, where the bands associated with various P–O(H) vibrations can be found. The three phosphonic acids adsorb onto boehmite by forming inner-sphere surface complexes. ATR-FTIR data indicates the presence of both protonated and deprotonated mononuclear surface species. In all cases, the surface-bound ions undergo protonation reactions as pH is decreased. The results are in good agreement with previously proposed surface complexation models.     

Adaptative and developmental responses to stress in Aspergillus nidulan

Development in the ascomycete A. nidulans is principally determined by environmental signals. Adaptability to oxidative stimuli can derive in changes of growth patterns and /or the activation of sexual or asexual reproductive cycles but this model fungus might also respond to high osmotic or salt concentrations, the redox state, the availability and quantity of carbon or nitrogen sources and the degree or quality of illumination. Since each cell within the colony follows a single morphogenetic program at a time, all these environmental cues might be sensed and integrated into a limited number of intracellular signals which, finally, would activate the required morphogenetic program and repress the others. This signaling mainly occurs through stress response pathways. The present review aims to summarize the available knowledge on how these pathways transduce environmental stimuli to mediate morphological changes in Aspergillus nidulans.     

Study of Electrochemical Processes with Coupled Homogeneous Chemical Reaction in Differential Pulse Voltammetry at Spherical Electrodes and Microhemispheres

Homogeneous chemical reactions coupled to oxidation‐reduction processes at electrode surfaces are very common in electrochemistry. In this paper we cope with the application of Differential Pulse Voltammetry at spherical electrodes and microhemispheres for the study of this kind of systems. Analytical expressions are deduced from which the influence of the different experimental variables is examined. Several diagnostic criteria for elucidation of the reaction mechanism from DPV peak parameters are given, as well as working curves for extraction of the kinetic rate constants of the chemical reaction.     

Emergence of Supramolecular Chirality by Flows

Hydrodynamic forces in stirred solutions induce chirality in some supramolecular species of J‐aggregates, as detected at the level of the electronic transition. However, the mechanism that explains the phenomenon remains to be elucidated, although the basic effect of hydrodynamic gradients of the shear rate is most probably the folding or bending of the nanoparticles in solution. Herein, we demonstrate a correlation between chiral flows in different regions of circular and square stirred cuvettes and the emergence of true circular dichroism (CD). The results show that chaotic flows lead to a racemic mixture of chiral shaped supramolecular species, and vortical flows to scalemic mixtures. In a magnetically stirred flask the descending and ascending flows are of different chiral sign and the CD reading depends on the weighting of these two flows of inverse chiral sign. The effect of the gradient of shear rates of the flows leading to chiral shape objects depends on the shape of the cuvette, which suggests that the flask shape and the controlled addition of reagents in defined regions of the stirred solutions may exert a control in self‐assembly processes.     

Study of ε-caprolactone polymerization by NIR spectroscopy

Near-infrared (NIR) spectroscopy is proposed for the in-line quantitative and kinetic study of the polymerization of ε-caprolactone and eventually to facilitate real-time control of the manufacturing process. Spectra were acquired with a fibre-optic probe operating in transflectance mode immersed in the reactor. The NIR data acquired were processed using a multivariate curve resolution alternating least squares (MCR-ALS) algorithm. The proposed method allows calculation of the concentration and spectral profiles of the species involved in the reaction. The key point of this method is the lack of reference concentrations needed to perform the MCR-ALS method. The use of an extended spectral matrix using both process and pure analyte spectra solves the rank deficiency. The concentration profiles obtained were used to calculate a kinetic fitting of the reaction, but the method was improved by applying kinetic constraints (hard modelling). The rate constants of batches at different temperatures and the energy of activation for this reaction were calculated. Whenever possible, the hard modelling combined with the MCR-ALS method improves the fit of the experimental data: the results show good correlation between the NIR and reference data and allow the collection of high-quality kinetic information on the reaction (rate constants and energy of activation).     

Miniature 10 kHz thermo-optic delay line in silicon

The scanning delay line is a key component of time-domain optical coherence tomography systems. It has evolved since its inception toward higher scan rates and simpler implementation. However, existing approaches still suffer from drawbacks in terms of size, cost, and complexity, and they are not suitable for implementation using integrated optics. In this Letter, we report a rapid scanning delay line based on the thermo-optic effect of silicon at λ = 1.3 μm manufactured around a generic planar lightwave circuit technology. The reported device attained line scan rates of 10 kHz and demonstrated a scan range of 0.95 mm without suffering any observable loss of resolution (15 μm FWHM) owing to depth-dependent chromatic dispersion.     

Cortical diversity in three species groups of Parmotrema sensu lato (Parmeliaceae,lichenized Ascomycota)

Conventional techniques for structural studies under light microscope were employed to describe and compare the upper cortex anatomy in three species groups of Parmotrema sensu lato. This study indicates that there is a pattern in the structure of the upper cortex in all the three groups of Parmotrema species studied here, and this pattern can be used to place each species group separately within the genus Parmotrema. Although the species of Parmotrema studied have palisade prosoplectenchymatous upper cortex, there are clear differences between the analyzed groups. The upper cortex of Parmotrema s. str. can be characterized by more elongated cells and very compressed hyphae with small interstices between them; the upper cortex of the species with reticular maculae is characterized by the presence of maculae produced by the organization of hyphae that rise towards to the upper cortex and that are not so compressed, while the upper cortex of the species with dimorphic rhizinae has less elongated almost-rounded cells without interstices or cracks but is generally accompanied by aeroplectenchyma. Besides, the first cell layer of the upper cortex presents differential staining by toluidine blue and the epicortex is tightly attached to it.     

Influence of thermoplastic starch plasticized with biodiesel glycerol on thermal properties of pp blends

Plastics have been used in short-life products, which have presented harmful consequences for the nature, because of the low degradation rate reached by the most common polyolefins. This work evaluates the mechanical and thermal properties of pure iPP, plasticized starch (TPS) with biodiesel (TPS_Bio) or commercial (TPS_Com) glycerols, and their blends (iPP/TPS_Plas). The addition of TPS_Plas caused an increasing on the cristallinity of iPP, mainly for the compositions 90/10 and 80/20, probably due to morphological alterations such as crosslinking, that may have modified the molecular arrangement of the iPP in the presence of glycerol.