Optimization of acid hydrolysis of sugarcane bagasse and investigations on its fermentability for the production of xylitol by Candida guilliermondii

The dilute-acid hydrolysis of sugarcane bagasse was optimized using a statistical experimental design resulting in hydrolysates containing 57.25 g/L of xylose, which were fermented with a high inoculum concentration (10 g/L of the yeast Candida guilliermondii IM/UFRJ 50088). The addition of urea reduced the time of conversion (t _C) to 75 h (without nitrogen source addition t _C>127 h), and, consequently, improving the rates of xylitol bioproduction. Fermentator experiments, using the optimized conditions, resulted in enhanced conversion rates, reducing t _C to 30 h. The stability of the yeast in the hydrolysate was also verified in a 480-h cultivation.     

Simultaneous Determination of Ascorbic Acid and Uric Acid by Using a PVC/TTF‐TCNQ Composite Electrode as Detector in a FIA System

A PVC/TTF‐TCNQ composite electrode has been employed as detector in a flow injection system. The proposed method allows the simultaneous detection of ascorbic acid (AA) and uric acid (UA) in mixtures by using a FIA system in a simple manner, without pre‐treatment or modified electrode. This method is based on the amperometric determination of (a) ascorbic acid at 0.15 V and (b) both analytes at 0.35 V, being the response linear in the range 1×10^?2–4×10^?4 M for both analytes with detection limits (S/N=3) of 1.2×10^?4 M and 8.1×10^?5 M for AA and UA, respectively.     

Separation of proteins with a molecular mass difference of 2 kDa utilizing preparative double-inverted gradient polyacrylamide gel electrophoresis under nonreducing conditions: application to the isolation of 24 kDa human growth hormone

A method for separating proteins with a molecular mass difference of 2 kDa using SDS-PAGE under nonreducing conditions is presented. A sample mixture containing several human growth hormone (hGH) isoforms was initially separated on a weak anion-exchange column. Fractions rich in 24 kDa hGH as determined by analytical SDS-PAGE were pooled and further separated by cation-exchange chromatography. The fractions pooled from the cation-exchange chromatography contained two hGH isoforms with a 2 kDa molecular mass difference according to SDS-PAGE analysis, 22 and 24 kDa hGH. The 22 and 24 kDa hGH were separated using continuous-elution preparative double-inverted gradient PAGE (PDG-PAGE) under nonreducing conditions. The preparative electrophoresis gel was composed of three stacked tubular polyacrylamide matrices, a 4% stacking gel, a 13-18% linear gradient gel, and a 15-10% linear inverted gradient gel. Fractions containing purified 24 kDa hGH were pooled and Western blot analysis displayed immunoreactivity to antihGH antibodies. PDG-PAGE provides researchers with an electrophoretic technique to preparatively purify proteins under nonreducing conditions with molecular mass differences of 2 kDa.     

Synthesis and crystallographic studies of two new 1,3,5‐triazines

The synthesis and characterization of two new 1,3,5‐triazines containing 2‐(aminomethyl)‐1H‐benzimidazole hydrochloride as a substituent are reported, namely, 2‐{[(4,6‐dichloro‐1,3,5‐triazin‐2‐yl)amino]methyl}‐1H‐benzimidazol‐3‐ium chloride, C₁₁H₉Cl₂N₆⁺·Cl^? ( 1 ), and bis(2,2′‐{[(6‐chloro‐1,3,5‐triazine‐2,4‐diyl)bis(azanediyl)]bis(methylene)}bis(1H‐benzimidazol‐3‐ium)) tetrachloride heptahydrate, 2C₁₉H₁₈ClN₉²⁺·4Cl^?·7H₂O ( 2 ). Both salts were characterized using single‐crystal X‐ray diffraction analysis and IR spectroscopy. Moreover, the NMR (¹H and ¹³C) spectra of 1 were obtained. Salts 1 and 2 have triclinic symmetry (space group P) and their supramolecular structures are stabilized by hydrogen bonding and offset π–π interactions. In hydrated salt 2 , the noncovalent interactions yield pseudo‐nanotubes filled with chloride anions and water molecules, which were modelled in the refinement with substitutional and positional disorder.     

A simple and fast micromethod for the analysis of polychlorinated biphenyls in air by sorbent enrichment and ultrasound-assisted solvent extraction

A combination of sorbent enrichment and ultrasound-assisted solvent extraction has been used to determine polychlorinated biphenyls in air. Analytes were sampled by pumping a known volume of air through a porous polymer (Tenax TA). The enriched adsorbent was transferred into a glass vial, and ultrasound-assisted extraction of the analytes was then performed in n-hexane. Quantification was carried out by using gas chromatography coupled to tandem mass spectrometry. Breakthrough volume of the sampling step was studied, indicating that 10 m³ of air could be processed without losses of the most volatile compounds. Good recoveries (75–96%) were obtained, and limits of detection at the sub ng m^–3 were achieved for all the analytes. The proposed method is very simple and fast, avoiding the use of large solvent volumes and time-consuming preconcentration steps.     

Visualizing defects and pore connectivity within metal–organic frameworks by X-ray transmission tomography

Metal–Organic Frameworks (MOFs) have the potential to change the landscape of molecular separations in chemical processes owing to their ability of selectively binding molecules. Their molecular sorting properties generally rely on the micro- and meso-pore structure, as well as on the presence of coordinatively unsaturated sites that interact with the different chemical species present in the feed. In this work, we show a first-of-its-kind tomographic imaging of the crystal morphology of a metal–organic framework by means of transmission X-ray microscopy (TXM), including a detailed data reconstruction and processing approach. Corroboration with Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) images shows the potential of this strategy for further (non-destructively) assessing the inner architecture of MOF crystals. By doing this, we have unraveled the presence of large voids in the internal structure of a MIL-47(V) crystal, which are typically thought of as rather homogeneous lattices. This challenges the established opinion that hydrothermal syntheses yield relatively defect-free material and sheds further light on the internal morphology of crystals.

TXM-tomography unraveled large macropore defects within a MIL-47(V) MOF crystal. These pores do not seem to be well connected and they show a preferential orientation.     

Selective hydrogenation of butadiene-styrene copolymers using a Ziegler-Natta type catalyst 2. Thermal properties

Three types of butadiene-styrene copolymers, diblock, triblock and random, were partially hydrogenated in their elastomeric units in order to determine the influence of hydrogenation extent on their thermal properties. The hydrogenation reactions were carried out using a Ziegler-Natta type catalyst and the extent of hydrogenation was evaluated by FTIR spectroscopic technique. The percentage of crystallinity was determined by differential scanning calorimetry (DSC), considering the low density polyethylene (LDPE) as reference since the saturation of elastomeric units with low content of 1,2-vinyl bonds gives a structure which resembles to LDPE, thus semi-crystalline polymers were obtained. On the other hand, the glass transition temperature (T_g) for the hydrogenated and non-hydrogenated copolymers as well as their heat of fusion, were also determined by DSC. An equation to evaluate the T_g of partially hydrogenated random copolymers is proposed considering both the saturated and unsaturated fractions. The thermo-oxidative behaviour of certain hydrogenated and non-hydrogenated copolymers was evaluated by thermogravimetric analyses (TGA). The results obtained by TGA suggest that a minimum saturation level is necessary in order to improve the thermo-oxidative resistance of the polymers.     

Activation thermodynamic parameters of binary mixtures of propionic acid ando-substituted anilines

Variations of densities and viscosities with temperature and composition are reported for binary liquid mixtures containing propionic acid+aniline (I),+o-toluidine (II),+o-anisidine (III), and+o-chloroaniline (IV). Entropies S _m and enthalpies H _m of activation as functions of the composition of the mixtures, as well as free energies of activation G _m at 10, 20, 30, 40, and 50°C and different compositions were calculated by means of Eyring's equation. The formation of activated complexes between the components of these binary mixtures is postulated and claimed to result from acid-base and hydrogen bonding exchange interactions.     

Field-amplified sample stacking and nonaqueous capillary electrophoresis determination of complex mixtures of polar aromatic sulfonates

Nonaqueous CE and field-amplified sample stacking have been used in the determination of complex mixtures of polar aromatic sulfonates (AS; mainly benzene- and naphthalenesulfonates) of environmental concern. The analytical procedure consists of an on-column aqueous sample enrichment, followed by the nonaqueous electrophoretic determination of stacked aromatic sulfonates. Various organic solvents were used as separation medium, acetonitrile and N-methylformamide gave the best results. Optimum capillary electrophoresis separation is obtained with ammonium acetate (25 mM) dissolved in N-methylformamide-methanol (90:10) as background electrolyte. This combined method was applied to the analysis of surface water samples spiked with selected aromatic sulfonates derivatives.     

A sum-over-histories account of an EPR(B) experiment

We analyze a variant of the EPRB experiment within a framework for quantum mechanics that rests on a radical interpretation of the sum over histories. Within this framework, reality is (just as classically) a single history, e.g. a definite collection of particles undergoing definite motions; and quantum dynamics appears as a kind of stochastic law of motion for that history, a law formulated in terms of non-classical probability-amplitudes. No state vectors enter this framework, and their attendant nonlocality is therefore absent as well.1. That is, before pair creations and annihilations were discovered. (The electronic and nuclear spins might also be regarded as new aspects of their kinematics. But perhaps spin is better construed, within the sum-over-histories framework, as a quality of a more dynamical character, namely as a generalized sort of probability-amplitude.)2. A possible escape would be the so-called Everett interpretation, in which the collapse never occurs, but its effects are supposed to be recovered via a more careful analysis of closed systems in which measurement-like processes take place. Among other things, this approach tends to lead either to the view that nothing really happens [1] or to the view that everything really happens [2] (which perhaps is not that different from the former view).3. For example, the rule, collapse occurs along the past light cone (in the Heisenberg picture), appears to be consistent.4. And Bell's inequality shows thatany theory formulated in terms of an instantaneous state evolving in time would encounter the same trouble. Indeed, the trouble shows up even more glaringly if one adapts Bell's argument to spin-1 systems, using the results of Kochen and Specker[10]. In order to use the Kochen-Specker results in the EPR manner one needs a scheme for measuring the relevant observables, but this can be accomplished by means of suitably concatenated Stern-Gerlach analyzers with recombining beams [13]. Then, as Allen Stairs has pointed out [14], even the perfect correlations become impossible to reproduce, and no reference to probability theory is needed to establish a contradiction with locality. Recently, an analogous experiment using three spin 1/2 particles instead of two spin 1 particles has also been given [15].5. No technical problem obstructs an extension to fermionic fields (indeed the functional integral formalism for Quantum Field Theory is probably the most popular at present), but the realistic interpretation of the individual histories seems to get lost. One way out would be if all fermions were composites or collective excitations of fields quantized according to bosonic commutation relations. Another would be if the particle formulation were taken as basic, with the complementary field formulation being merely a mathematical artifice (at least for fermions).6. In the approach of Gell-Mann-Hartle and Griffiths for example, only a small subset of the possible partitions is granted meaning, in such a way that all interference terms are suppressed and quantum probabilities reduce to classical ones.7. In stating these rules we consider an idealized situation in which the spatio-temporal indeterminacy of particle-locationwithin a given one of our trajectories is ignored; or if you prefer, you can take the experiment as only a Gedanken one affording a simplified illustration of how EPR-like correlations are understood within the sum-over-histories framework. In this connection recall also that the semiclassical propagator is in fact exact for a free particle.8. This can be interpreted either as part of the specification of the initial conditions, or (as suggested by a referee) merely as an example of relativization of probabilities.9. Thus a state vector may be defined as an equivalence-class of sets of partial histories.10. One such generalization applies to open systems, for example to a particle in contact with a heat reservoir. For this example see [11], wherein the two-way path formalism of §5 above is used, and the influence of the reservoir results in an effective dynamics for the particle in which the forward and backward portions of its world-line are coupled to each other by a certain interaction term in the amplitude. In this type of situation a density-operator (though not a state vector ) can still be introduced, but it no longer summarizes all the relevant information about the past (and correspondingly its evolution lacks the Markov property that(t + dt) is determined by(t) alone). For quantum gravity, it may be that not even such a non-Markov will be exactly definable, and only the global probabilities themselves will make sense.11. Ironically it is just this property of the amplitudes which, as mentioned above, makes possible the introduction of the state vectors whose collapse then introduces such a strong appearance ofnonlocality into the theory.