But‐2‐ene‐1,4‐diamine and But‐2‐ene‐1,4‐diol as Donors for Thermodynamically Favored Transaminase‐ and Alcohol Dehydrogenase‐Catalyzed Processes

Both cis‐ and trans‐but‐2‐ene‐1,4‐diamines have been prepared and efficiently applied as sacrificial cosubstrates in enzymatic transamination reactions. The best results were obtained with the cis‐diamine. The thermodynamic equilibrium of the stereoselective transamination process is shifted to the amine formation due to tautomerization of 5H‐pyrrole into 1H‐pyrrole, achieving high conversions (78–99%) and enantiomeric excess (up to >99%) by using a small excess of the amine donor. Furthermore, when the reaction proceeded, a strong coloration was observed due to polymerization of 1H‐pyrrole. A structurally related compound, cis‐but‐2‐ene‐1,4‐diol, has been utilized as cosubstrate in different alcohol dehydrogenase (ADH)‐mediated bioreductions. In this case, high conversions (91–99%) were observed due to a lactonization process. Both strategies are convenient from both synthetic and atom economy points of view in the production of valuable optically active products.

     

Dynamic Reductive Kinetic Resolution of Benzyl Ketones using Alcohol Dehydrogenases and Anion Exchange Resins

Dynamic reductive kinetic resolutions of racemic 3‐arylalkanones have been performed by the proper combination of an alcohol dehydrogenase and a basic anionic resin. The best results were found for the bioreduction with the alcohol dehydrogenase type A from Rhodococcus ruber DSM 44541 overexpressed in Escherichia coli (E. coli/ADH‐A) and the commercially available evo‐1.1.200, while the Amberlite IRA‐440 C and the DOWEX‐MWA‐1 resins allowed efficient in situ racemizations. Reaction conditions were optimized in terms of enzyme source and loading, type and amount of resin, pH, temperature and reaction times, obtaining a series of (R,R)‐substituted propan‐2‐ols with good conversions and both diastereoselectivity and stereoselectivity. As a proof of concept, the subsequent intramolecular cyclization of a selected propan‐2‐ol substrate afforded a valuable isochroman heterocycle without any loss of the optical purity.

     

Oxidation of activated carbon by dry and wet methods: Surface chemistry and textural modifications

The effects of dry and wet oxidation treatments of activated carbon (AC) on the surface chemistry and porous structure are studied. Using cherry stones (CS), AC was first prepared by carbonization at 900 °C for 2 h in N₂ and activation at 850 °C for 2 h in CO₂. Then, the resulting AC was oxidized in O₂(air) or O₃ atmosphere and with HNO₃ and H₂O₂ solutions. The acidic-basic surface sites were analyzed by FT-IR spectroscopy, Boehm method, and pH of the point of zero charge (pH_pzc) and the porous structure by N₂ adsorption and mercury porosimetry. It has been found that the oxidizing agent, under specific reaction conditions, rather than whether it was a gas or a solute in aqueous solution, is the main factor that controls the changes produced in the surface chemistry and porous structure of AC. O₃ and HNO₃ are the most effective oxidants to form acidic oxygen surface groups. However, the content of basic groups decreases for the four oxidants, the effect being much stronger for HNO₃. A microporosity reduction is also observed, which is more important for O₂(air) and especially for HNO₃ than for O₃ and H₂O₂. The percentage of microporosity loss is as high as 43.3 for HNO₃. Mesoporosity significantly develops, whereas macroporosity usually remains practically unchanged. Dry oxidation of AC at 100 °C in O₃ has proved to be the most promising method to increase the content of acidic oxygen surface groups in the material without greatly decreasing the content of basic sites and microporosity and with a significant mesoporosity development.     

Polycyclic N-benzamido imides with potent activity against vaccinia virus

The synthesis and antiviral activity of a series of novel polycyclic analogues of the orthopoxvirus egress inhibitor tecovirimat (ST‐246) is presented. Several of these compounds display sub‐micromolar activity against vaccinia virus, and were more potent than cidofovir (CDV). The more active compounds were about 10‐fold more active than CDV, with minimum cytotoxic concentrations above 100 μM . Chemical manipulations of the two carbon–carbon double bonds present in the compounds were carried out to further explore the structure–activity relationships of these new polycyclic imides. Hydrogenation of the two carbon–carbon double bonds decreases antiviral activity, whereas either cyclopropanation or epoxidation of the double bonds fully eliminates the antiviral activity.     

A Multiplex Assay to Assess the Transaminase Activity toward Chemically Diverse Amine Donors

The development of methods to engineer and immobilize amine transaminases (ATAs) to improve their functionality and operational stability is gaining momentum. The quest for robust, fast, and easy-to-use methods to screen the activity of large collections of transaminases, is essential. This work presents a novel and multiplex fluorescence-based kinetic assay to assess ATA activity using 4-dimethylamino-1-naphthaldehyde as an amine acceptor. The developed assay allowed us to screen a battery of amine donors using free and immobilized ATAs from different microbial sources as biocatalysts. As a result, using chromatographic methods, 4-hydroxybenzylamine was identified as the best amine donor for the amination of 5-(hydroxymethyl)furfural. Finally, we adapted this method to determine the apparent Michaelis-Menten parameters of a model immobilized ATA at the microscopic (single-particle) level. Our studies promote the use of this multiplex, multidimensional assay to screen ATAs for further improvement.     

Lessening polygalacturonase activity in a commercial enzyme preparation by exposure to pulsed electric fields

The effect of high-intensity pulsed electric field (HIPEF) treatments on polygalacturonase (PG) activity in an aqueous solution of a commercial enzyme preparation was evaluated. HIPEF treatments reduced PG activity notably. Exponentially decaying pulses of 40 and 160 µs generated by a laboratory scale device were applied in a batch processing and bipolar mode. Electric fields ranged from 5.18 to 19.39 kV/cm. The number of pulses ranged up to 400. Temperature was always below 25 °C. Maximum inactivation of PG activity (98%) required 32.4 ms HIPEF treatment at 10.28 kV/cm. PG activity depleted exponentially because of HIPEF treatments. The first order rate constants ranged from 32 to 590 µs ^-1 and increased exponentially with electric field intensity. PG activity decreased exponentially with input electric energy density.     

Assessment of the suitability of soil amendments to reduce 137Cs and 90Sr root uptake in meadows

In situ remediation strategies are an alternative approach in the management of radioactive contaminated areas, especially when based on modification of soil properties by the addition of amendments. Here, this strategy is applied to reduce 137Cs and 90Sr soil-plant transfer in meadows from areas of Russia, Belarus, and Ukraine affected by the Chernobyl fallout. Meadows were established on podzolic and peaty soils. Amendments covered a wide range of materials, such as loamy and sandy soils, polygorskite clay, phosphorite, turf, and sapropel. Field experiments showed the poor efficiency of most of the materials: only the polygorskite clay provoked a notable reduction (1.5-2-fold) in 137Cs root uptake. Subsequent laboratory characterization showed the lack of significant changes in the radiocesium interception potential and soil solution composition in the amended soils, a fact that helped to explain the lack of effect on the reduction of transfer. Moreover, a laboratory methodology based on the quantification of the adsorption potential of the amendments and the reversibility of the adsorption process was applied. This methodology was first proposed for the correct selection of the suitable materials to be used to decrease radionuclide root uptake in future remediation actions and then validated with data of the previous field experiments.     

Preparation of composites of laponite with alginate and alginic acid polysaccharides

Polymer/clay composites have several uses in fields such as engineering, agriculture, ceramics, surface coatings, absorbent materials, pharmaceuticals or catalysis. Polysaccharides, such as alginate and its acid derivatives, are biocompatible and biodegradable polymers, effective in the production of adsorbent systems, for encapsulation and controlled release of active ingredients such as drugs and fertilizers. In this work, alginate polysaccharide and alginic acid were used to form composites with laponite, both with the original clay or with clay previously functionalized with 3‐aminopropyltriethoxysilane. The properties of the composites prepared from laponite or functionalized laponite and alginic acid or alginate were compared. The interaction of laponite with alginic acid leads to composites with strong disorder in the clay structure. In all cases, composites with high contents of polysaccharides, with good thermal and mechanical properties, are obtained. Laponite‐derived composites showed high adsorption capability for Cr(III) and methylene blue from aqueous medium. Copyright © 2012 Society of Chemical Industry     

Rapid determination of soluble solids content and acidity of Black currant (Ribes nigrum L.) juice by mid-infrared spectroscopy performed in series

Black currant juice quality is a prime importance for growers and industrials. Such quality relies on the empirical and destructive measurements of soluble solids content and acidity. These measurements are time consuming and expensive. The serial analysis of the Black currant juice quality could allow the valuation of the product for the producer and saving of time for the manufacturer. Our objective was to develop predictive models of soluble solids content and acidity based on the mid-infrared spectroscopy performed in series.We showed that infrared spectroscopy allowed determining efficiently the quality of Black currant juices and that such technique could be performed in series. Soluble solids content were determined with a R²-value of 0.97 and an RMSECV of 1.14°Brix for a range of values comprised between 12.9°Brix and 16.42°Brix. Acidity content was determined with a R²-value of 0.96 and an RMSECV of 2.61 g L⁻¹ in a large range of values comprised between 14.87 g L⁻¹ and 36.27 g L⁻¹.These results allow asserting that the soluble solids content and the acidity of Black currant juice can be accurately determined by infrared spectroscopy. Furthermore, a large number of measures can be performed in series, what opens perspectives for a practical application.     

Failures of harbour walls at Malaga and Barcelona

The paper describes the failure of harbour walls which occurred at Malaga on 4th July 2004 and at Barcelona on 1st January 2007, associated with an inadequate consideration of the ground conditions in the light of the marine environment. At Malaga, there was an existing breakwater hence the new harbour was protected from the effect of the waves while at Barcelona, the construction of the quay wall proceeded at a faster rate than the breakwater. In both cases the wharf backfill was placed rapidly on the soft muds, progressing from the inland side. The paper discusses the importance of an overview including the ground investigation, engineering design, construction method and speed of construction.