Improved sulfuric acid decrystallization of wheat straw to obtain high yield carbohydrates

Wheat straw is an abundant residue of agriculture which is increasingly considered as a feedstock for the production of fuels, energy and chemicals. The concentrated acid hydrolysis of wheat straw has been investigated in this work. Hemicellulose and cellulose have been efficiently converted into monomers of pentoses and glucose in high yields by a one-pot decrystallization-hydrolysis procedure. This process differs from usual concentrated acid biomass fractionation methodologies as a low quantity of acid is used and the supplementary use of a costly acid is not necessary to yield efficiently carbohydrates. The influence of the acid native concentration, and of the time of the decrystallization step have been studied so as to optimise yields of carbohydrates using a minimum of sulfuric acid so as to preserve a potential market value of the process. One can also imagine that this procedure will not impact dramatically the subsequent purification costs. In view of the growing importance of renewable resource-based molecules in the chemical industry, and the necessity to produce fermentable substrate for biofuels, this approach may open a new avenue for the use of wheat straw as raw material for various applications.     

Synchrotron fourier transform infrared microspectroscopy: A new tool to monitor the fate of organic contaminants in plants

FTIR microspectroscopy, with synchrotron radiation as a source, was used for the first time to study changes in plant structure induced by organic contaminants. Sunflower (Helianthus annuus L.) plants were grown hydroponically in the presence of benzotriazole. Changes in the plant structure due to uptake, incorporation, and/or transformation of benzotriazole were observed. False color intensity maps of benzotriazole treated secondary root sections showed changes in plant structure, as well as the presence of aromatic CH peaks due to incorporation of benzotriazole within the plant. The presence of the characteristic benzotriazole CH out-of-plane bending mode suggests that the contaminant aromatic ring remains intact upon the uptake by the plant. Simultaneously, the changes in the lignin structure suggest that the plant suffered damage by the uptake of the benzotriazole. Spectral variations between the untreated and benzotriazole treated sunflowers were uncovered using principal components analysis (PCA). PCA also revealed clustering according to the different benzotriazole treatments.     

Practical asymmetric synthesis of alpha-branched 2-piperazinylbenzylamines by 1,2-additions of organometallic reagents to N-tert-butanesulfinyl imines

[reaction: see text] 2-[4-(tert-Butoxycarbonyl)piperazinyl]benzylidene-tert-butanesulfinamides underwent nucleophilic 1,2-addition with different organometallic reagents to give highly diastereomerically enriched adducts. X-ray crystallography of the resulting alpha-branched N-Boc-2-piperazinylbenzyl-tert-butanesulfinamides confirms different mechanisms depending on the organometallic reagent used. Differential deprotection of the N-Boc and the tert-butanesulfinamides was investigated, and the dehydration byproducts have been identified and characterized. To avoid the formation of byproducts in the acidic deprotection step, the N-tert-butanesulfinamide group was converted to the corresponding N-tert-butanesulfonamide (Bus), which allowed for clean orthogonal deprotection. The efficient synthesis and deprotection of the N-Boc-2-piperazinylbenzyl-tert-butanesulfinamides herein described constitutes an attractive method for extensive structure-activity studies in the search for novel ligands of the human melanocortin 4 receptor.     

A CTRW-based model of time-resolved fluorescence lifetime imaging in a turbid medium

We develop an analytic model of time-resolved fluorescent imaging of photons migrating through a semi-infinite turbid medium bounded by an infinite plane in the presence of a single stationary point fluorophore embedded in the medium. In contrast to earlier models of fluorescent imaging in which photon motion is assumed to be some form of continuous diffusion process, the present analysis is based on a continuous-time random walk (CTRW) on a simple cubic lattice, the objective being to estimate the position and lifetime of the fluorophore. This can provide information related to local variations in pH and temperature with potential medical significance. Aspects of the theory were tested using time-resolved measurements of the fluorescence from small inclusions inside tissue-like phantoms. The experimental results were found to be in good agreement with theoretical predictions provided that the fluorophore was not located too close to the planar boundary, a common problem in many diffusive systems.     

Straightforward synthesis of (S)- and (R)-alpha-trifluoromethyl proline from chiral oxazolidines derived from ethyl trifluoropyruvate

[Structure: see text] A concise synthesis of both enantiomers of alpha-Tfm-proline and (S)-alpha-Tfm-prolinol from ethyl trifluoropyruvate is reported. The key step is a diastereoselective allylation reaction of ethyl trifluoropyruvate and (R)-phenylglycinol-based oxazolidines or imine. The lactone obtained by cyclization of the resulting hydroxy ester proved to be a valuable intermediate for the synthesis of (S)-alpha-Tfm-allylglycine and (S)-alpha-Tfm-norvaline in enantiopure form.     

Design of self-cleaning TiO2 coating on clay roofing tiles

The phenomenon of heterogeneous photocatalysis takes place in the degradation process of many organic contaminants on solid surfaces. Photocatalysis is based on the excitation of the semiconductor by irradiation with supraband gap photons and the migration of electron-hole pairs to the surface of the photocatalysts, leading to the reaction of the holes with adsorbed H₂O and OH^? to form hydroxyl radicals. Due to the stability and photosensitivity of TiO₂ semiconductors, this system is well studied and is of great interest from an ecological and industrial point of view for use in the field of building materials. Clay roofing tiles, due to their long-term exploitation, are subject to physical, chemical and biological degradation that leads to deterioration. Ceramic systems have a high percentage of total porosity and considering their non-tolerance of organic coating, the use of surface active materials (SAM) that induce porosity in TiO₂ coatings is of vital significance. Photocatalytic coatings applied on clay roofing tiles under industrial conditions were designed by varying the quantity of TiO₂ (mass/cm²) on the tile surface (thin and thick TiO₂ layer). The positive changes in specific surface area and mesopore structure of the designed coatings were made by the addition of PEG 600 as a surface active material. It was shown that a thin photocatalytic layer (0.399 mg suspension/cm² tile surface), applied onto ceramic tiles under industrial conditions, had better photocatalytic activity in methylene blue decomposition, hydrophilicity and antimicrobial activity than a thick photocatalytic coating (0.885 mg suspension/cm²).     

Minimal kinematic boundary conditions for simulations of disordered microstructures

In simulations of representative volume elements (RVEs) of materials with disordered microstructures, commonly used rigid and periodic boundary conditions (BCs) introduce additional constraints, causing: (i) boundary effects, (ii) unrealistic stiff response, (iii) artificial wavelengths in the solution fields, and (iv) suppression of solutions with localized deformation that otherwise may occur in the simulation. In this paper we define the minimal kinematic boundary conditions such that only the desired overall strain is imposed on the RVE, with no other undesirable constraints. We prove that such BCs result in a unique solution for the linear elastic case, and that the uniqueness for nonlinear problems is dependent on the pointwise positive definiteness of the incremental stiffness tensor. Upon incorporating the minimal BCs into the finite element framework, we consider, as an example, two-dimensional, linear elastic, disordered polycrystals and perform a systematic study of the effects of boundary conditions while varying the RVE size and controlling the sampling error. The results demonstrate that the minimal BCs, applicable to a RVE of any shape, are superior to other BCs, in that they give more realistic overall behaviour, reduce the required size of the RVE, and eliminate the superficial wavelengths in the solution field, ubiquitous in simulations with other boundary conditions.     

A Power Interruption Technique for Investigation of Temperature Difference in Stabilized Low Direct-Current Arc Burning in Pure Argon on Atmospheric Pressure

Plasma of argon stabilized arc column, in a current range 3-11 A, is investigated using emission spectrometric diagnostic techniques. Temperatures are evaluated using several methods： argon line to adjacent recombinational continuum intensity ratio, absolute emissivity of argon line, measurement of electron number density, and power interruption. Electron number density is evaluated from absolute emissivity of recombinational continuum. The difference between electron Te and heavy particle Th temperature ranged from 4500 K for 3 A to 2300 K for 11A arc current. By comparing the present with the previously obtained results, using the same arc device but with the introduction of water aerosol, it is concluded that water aerosol reduces the difference Te - Th and brings plasma closer to the partial thermodynamic equilibrium state.     

Structural effects on interconversion of oxygen-substituted bisketenes and cyclobutenediones

Cyclobutenediones 5 disubstituted with HO (a), MeO (b), EtO (c), i-PrO (d), t-BuO (e), PhO (f), 4-MeOC6H4O (g), 4-O2NC6H4O (h), and 3,4-bridging OCH2CH2O (i) substituents upon laser flash photolysis gave the corresponding bisketenes 6a-i, as detected by their distinctive doublet IR absorptions between 2075 and 2106 and 2116 and 2140 cm-1. The reactivities in ring closure back to the cyclobutenediones were greatest for the group 6b-e, with the highest rate constant of 2.95 x 10(7) s-1 at 25 degrees C for 6e (RO = t-BuO) in isooctane, were less for 6a (RO = OH, k = 2.57 x 10(6) s-1 in CH3CN), while 6f-i were the least reactive, with the lowest rate constant of 3.8 x 10(4) s-1 in CH3CN for 6h (RO = 4-O2NC6H4O). The significantly reduced rate constants for 6f-i are attributed to diminution of the electron-donating ability of oxygen to the cyclobutenediones 5f-h by the ArO substituents compared to alkoxy groups and to angle strain in the bridged product cyclobutenedione 5i. The reactivities of the ArO-substituted bisketenes 6f-h in CH3CN varied by a factor of 50 and gave an excellent correlation of the observed rate constants log k with the sigma p constants of the aryl substituents. Computational studies at the B3LYP/6-31G(d) level of ring-closure barriers are consistent with the measured reactivities. Photolysis of squaric acid (5a) in solution provides a convenient preparation of deltic acid (7).     

The Microstructural Changes of Cobalt Powder in Consequence of Cold Pressing Process

The application of pressure as a technique for obtaining dense and mechanically strengthen materials has been investigated from the structural aspect by the use of X-Ray Powder Diffraction (XRPD) and Scanning Tunneling Microscopy (STM).