Enhancing the enzymatic hydrolysis of cellulosic materials using simultaneous ball milling

One of the limiting factors restricting the effective and efficient bioconversion of softwood-derived lignocellulosic residues is the recalcitrance of the substrate following pretreatment. Consequently, the ensuing enzymatic process requires relatively high enzyme loadings to produce monomeric carbohydrates that are readily fermentable by ethanologenic microorganisms. In an attempt to circumvent the need for larger enzyme loadings, a simultaneous physical and enzymatic hydrolysis treatment was evaluated. A ball-mill reactor was used as the digestion vessel, and the extent and rate of hydrolysis were monitored. Concurrently, enzyme adsorption profiles and the rate of conversion during the course of hydrolysis were monitored. α-Cellulose, employed as a model substrate, and SO₂-impregnated steam-exploded Douglas-fir wood chips were assessed as the cellulosic substrates. The softwood-derived substrate was further posttreated with water and hot alkaline hydrogen peroxide to remove >90% of the original lignin. Experiments at different reaction conditions were evaluated, including substrate concentration, enzyme loading, reaction volumes, and number of ball beads employed during mechanical milling. It was apparent that the best conditions for the enzymatic hydrolysis of α-cellulose were attained using a higher number of beads, while the presence of air-liquid interface did not seem to affect the rate of saccharification. Similarly, when employing the lignocellulosic substrate, up to 100% hydrolysis could be achieved with a minimum enzyme loading (10 filter paper units/g of cellulose), at lower substrate concentrations and with a greater number of reaction beads during milling. It was apparent that the combined strategy of simultaneous ball milling and enzymatic hydrolysis could improve the rate of saccharification and/or reduce the enzyme loading required to attain total hydrolysis of the carbohydrate moieties.     

Poly(N‐Bromobenzene‐1,3‐Disulfonylamide), N,N,N′,N′‐Tetrabromobenzene‐1,3‐Disulfonylamide and DABCO‐Bromine Complex: As Novel Reagents for the Oxidative Coupling of Thiols to Disulfides

An efficient method for the oxidative coupling of thiols to their corresponding disulfides by new reagents poly(N‐bromobenzene‐1,3‐disulfonylamide) PBBS , N,N,N′,N′‐tetrabromobenzene‐1,3‐disulfonylamide TBBDA and DABCO‐bromine complex is described. The reaction was applicable to a variety of thiols with high chemoselectivity.     

Tribromoisocyanuric Acid (TBCA) and Oxone®‐MX Systems as Oxidizing Agents: Oxidative Coupling of Thiols to Their Corresponding Disulfides under Mild and Heterogeneous Conditions

Tribromoisocyanuric acid (TBCA) and Oxone^®‐MX systems were used as effective oxidizing agents for the oxidation of thiols to their corresponding disulfides under mild conditions at room temperature with good to excellent yields.     

Solid Phase Extraction and Flame Atomic Absorption Spectrometric Determination of Trace Amounts of Zinc and Cobalt Ions in Water Samples

A simple and rapid method for the preconcentration of Co²⁺ and Zn²⁺ as their 2-guanidino-benzimidazole chelates is proposed using an octadecyl silica cartridge. The retained analytes were recovered with a mixture of 5mL of 0.01M HNO₃ and 5mL of methanol. The metal ions in the effluent were determined by flame atomic absorption spectrometry. The effect of different parameters, such as sample matrix, amount of ligand, type of eluent for elution of ions from cartridge, flow rates of sample solution and eluent, breakthrough volume, and limit of detection, were evaluated. The effects of various cationic and anionic interferences on the percent recovery of Co²⁺ and Zn²⁺ were also studied. Quantitative extraction efficiencies were obtained by elution of the cartridge with a minimal amount of solvent. Hence, with a typical preconcentration factor of 50, the limits of detections of the proposed method are 0.26 and 1.62ngmL^–1 for Zn²⁺ and Co²⁺, respectively. The method was applied to the determination of zinc and cobalt ions in different water samples.     

Microemulsion-based synthesis of CeO(2) powders with high surface area and high-temperature stabilities

Pure ceria powders, CeO(2), were synthesized in heptane-microemulsified aqueous solutions of CeCl(3) or Ce(NO(3))(3) stabilized by AOT (sodium bis(2-ethylhexyl) sulfosuccinate), DDAB (di-n-didodecyldimethylammonium bromide), or DDAB + Brij 35 surfactant mixtures. Micellar DTAB (n-dodecyltrimethylammonium bromide) and vesicular DDAB systems were also used as media for generating CeO(2). Characterization of the powders by X-ray powder diffractometry, laser-Raman spectroscopy, and Fourier transform infrared spectroscopy revealed that in the presence of surfactants almost-agglomerate-free nanosized crystallites (6-13 nm) of anionic vacancy-free cubic CeO(2) were produced. In the absence of surfactants 21-nm-sized crystallites were formed, comparing with the 85-nm-sized crystallites when cubic CeO(2) was created via thermal decomposition of cerium oxalate. Surface characterization, by X-ray photoelectron spectroscopy, N(2) sorptiometry, and high-resolution electron microscopy showed AOT- or (DDAB + Brij 35)-stabilized microemulsions to assist in formation of crystallites exposing surfaces of large specific areas (up to ca. 250 m(2)/g) but of low stability to high-temperature calcination (28-13 m(2)/g at 800 degrees C). In contrast, the double-chained DDAB was found to generate cubic CeO(2) crystallites of lower initial surface areas (144 (microemulsion) to 125 (vesicles) m(2)/g)) but of higher thermal stability (55-45 m(2)/g at 800 degrees C). Hence, the latter cerias could be considered as appropriate components for total oxidation (combustion) catalysts.     

Stereoselective synthesis of 4-hydroxy-2-phenylproline framework

Highly diastereoselective (>20:1) bromo-lactonization of N-sulfonyl-2-allyl-2-phenylglycine methyl ester (11) was observed. Successive treatment of the chiral lactone with MeONa gave the desired (2S,4R)-4-hydroxy-2-phenylproline derivative in high yield without erosion of the diastereoselectivity. The starting chiral non-racemic compound (5) was prepared from the racemic 2-phenylglycine using a classical kinetic resolution (crystallization), an asymmetric phase transfer alkylation, and an enzyme-catalyzed kinetic resolution.     

Monitoring nitrite with optical sensing films

A new, low-cost nitrite sensor was developed by immobilizing a direct indicator dye in an optical sensing film for food and environmental monitoring. This sensor was fabricated by binding Safranine O to a cellulose acetate film that had previously been subjected to an exhaustive base hydrolysis. The membrane has good durability (>12 months) and a short response time (<8 s). Nitrite can be determined for the range of 0.005-2.00 μg ml⁻¹ with 3δ detection limits of 0.001 μg ml⁻¹. The method is easy to perform and uses acetylcellulose as a carrier. The reagents used for the activity of the cellulose support are inexpensive, non-toxic and widely available.     

4,4-Acetalidine-bis-(3-methyl isoxazolone-5) as a new colorimetric reagent for the determination of palladium and uranium

Summary Palladium and uranium react with 4,4-acetalidine-bis-(3-methyl isoxazolone-5) in acid medium to give yellow color having a visual limit of identification at 2 and 15g per ml. This color reaction provides the basis of a new method for colorimetric determination of palladium and uranium. Copper also gives yellow color but it cannot be determined with this color reaction because the color intensity is not stable. The maximum tolerable limit of various ions is reported.

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Zusammenfassung Pd und U reagieren in saurem Milieu mit 4,4-Acetalidin-bis-(3-methyl-isoxazolon-5) unter Gelbfärbung mit einer Erfassungsgrenze von 2 bzw. 15g/ml. Diese Farbreaktion dient als Grundlage für eine neue kolorimetrische Methode für Pd und U. Cu gibt zwar auch eine Gelbfärbung, kann aber damit nicht bestimmt werden, da die Farbintensität nicht beständig ist. Die maximal tolerierbare Menge der Fremdionen wird angegeben.

     

Two‐Dimensional Holo‐ and Hemidirected Lead(II) Coordination Polymers: Synthetic,Spectroscopic, Thermal,and Structural Studies of [Pb(μ‐SCN)2(μ‐ebp)1.5]n and {[Pb(μ‐OAc)(μ‐ebp)](ClO4)}n (ebp=4,4′‐[(1E)‐Ethane‐1,2‐diyl]bis[pyridine]; OAc=Acetato)

Two new coordination polymers of Pb^II complexes with bridging 4,4′‐[(1E)‐ethane‐1,2‐diyl]bis[pyridine] (ebp), thiocyanato, and acetato ligands, [Pb(μ‐SCN)₂(μ‐ebp)_1.5]_n ( 1 ) and {[Pb(μ‐OAc)(μ‐ebp)](ClO₄)}_n ( 2 ), were synthesized and characterized by elemental analysis, FT‐IR, ¹H‐ and ¹³C‐NMR, thermal analysis, and single‐crystal X‐ray diffraction. In 1 , the Pb²⁺ ions are doubly bridged by both the ebp and the SCN⁻ ligands into a two‐dimensional polymeric network. The seven‐coordinate geometry around the Pb²⁺ ion in 1 is a distorted monocapped trigonal prism, in which the Pb²⁺ ions have a less‐common holodirected geometry. In 2 , the Pb²⁺ ions are bridged by AcO⁻ ligands forming linear chains, which are also further bridged by the neutral ebp ligands into a two‐dimensional polymeric framework. The Pb²⁺ ions have a five‐coordinate geometry with two N‐atoms from two ebp ligands and three O‐atoms of AcO⁻. Although ClO acts as a counter‐ion, it also makes weak interactions with the Pb²⁺ center. The arrangement of the ligands in 2 exhibits hemidirected geometry, and the coordination gap around the Pb²⁺ ion is possibly occupied by a configurationally active lone pair of electrons.     

Metal chelates of heterocyclic nitrogen-containing ketones,Part XXII. Spectroscopic studies on rhodium(III) complexes of phenyl-2-picolylketone-2-pyridyl hydrazone

Summary Mono, bis and tris complexes of rhodium(III) with phenyl-2-picolylketone-2-pyridyl hydrazone (PPKPyH) have been characterized. In every case, the imino-proton of PPKPyH shows marked acidity associated with the coordination to rhodium(III). Electronic spectra show that all complexes are octahedral. The B-values suggest a strong covalency in the metal-ligand -bond and the Dq-values indicate a medium-strong ligand field. The magnetic susceptibility indicates that PPKPyH forms low-spin complexes with rhodium(III).¹H n.m.r. spectra show that the tris(ligand) complexes arecis isomers. I.r. spectra show that the ligand is neutral or monobasic tridentate or bidentate. Far i.r. studies show that [Rh(PPKPyH)X₃] · 2 H₂O (X = Cl, Br or I) aremer isomers. The effect of pH variation on the rection products is also discussed.