Biology of the red mullet mullus surmuletus (mullidae) off the Canary Islands, Central-East Atlantic

The biology of red mullet Mullus surmuletus was studied from collections taken off the Canary Islandsbetween January 1991 and September 1993. Total length ranged from 12 to 33 cm, mainly between 15 and 21cm. Males ranged from 14 to 26 cm and females from 14 to 33 cm. Females dominated the larger size-classes (>18 cm). The overall ratio of males to females was 1:2.3. The reproductive period extended from February toMay, spawning peaking in March and April. The total length at 50% maturity was 16.6 cm for the whole population.The length-mass relationship for all individuals can be described by the parameters a = 0.0074 and b = 3.1826. Fish aged 0.8 years were present in the samples. The parameters of the Von Bertalanffy growth equation obtained for all individuals were: L‡ = 35.71 cm and k = 0.22.year-1. Significant differences were found in the growth parameters between males and females. The rates of total mortality Z, natural mortality M and fishing mortality F were 1.25, 0.55 and 0.70.year-1 respectively. The estimated total length at first capture was 15.74 cm

Combinatorial Assortment Optimization

Assortment optimization refers to the problem of designing a slate of products to offer potential customers, such as stocking the shelves in a convenience store. The price of each product is fixed in advance, and a probabilistic choice function describes which product a customer will choose from any given subset. We introduce the combinatorial assortment problem, where each customer may select a bundle of products. We consider a model of consumer choice where the relative value of different bundles is described by a valuation function, while individual customers may differ in their absolute willingness to pay, and study the complexity of the resulting optimization problem. We show that any sub-polynomial approximation to the problem requires exponentially many demand queries when the valuation function is XOS, and that no FPTAS exists even for succinctly-representable submodular valuations. On the positive side, we show how to obtain constant approximations under a "well-priced" condition, where each product's price is sufficiently high. We also provide an exact algorithm for $k$-additive valuations, and show how to extend our results to a learning setting where the seller must infer the customers' preferences from their purchasing behavior

Norcoclaurine Synthase-Mediated Stereoselective Synthesis of 1,1'-Disubstituted, Spiro- and Bis-Tetrahydroisoquinoline Alkaloids

The Pictet–Spenglerase norcoclaurine synthase (NCS) catalyzes the formation of (S)-norcoclaurine, an important intermediate in the biosynthetic pathway of benzylisoquinoline alkaloids. NCS has been used as a biocatalyst with meta-hydroxy phenethylamines and aldehydes for the preparation of single-isomer tetrahydroisoquinoline alkaloids (THIAs). Recently, it was also reported that some ketones can be accepted as substrates, including 4-substituted cyclohexanones and phenyl acetones. Here, we report the use of wild-type NCS and selected variants with aliphatic, cyclic, α-substituted cyclic, heterocyclic, and bicyclic ketones to access challenging non-natural THIAs. Remarkably, fused bicyclic ketones as well as diketones could also be accepted by some of the NCS variants, and in silico modeling was used to provide insights into the rationale for this

Inactivation of high concentration of pathogens in land-applied food industry sludge

In Mexico, as in other developing countries, the most important pollution and management problems of food-processing sludge are the high levels of pathogen microorganisms within the sludge and the lack of sites for its disposal. The aims of this study were to evaluate the effect of calcium oxide in the inactivation of pathogenic microorganisms and the subsequent use of the resulting product in an agricultural application at various agronomic rates. Stabilisation tests were done in a hermetically closed fibreglass reactor with 1.5 . capacity, using physicochemical sludge with concentrations of 4, 8 and 12% of total solids (TS) and contact times of 30, 60 and 90 min. At the end of each treatment, the raw and treated sludge quality was evaluated. Recommended doses for Class A biosolids production were 20, 10 and 8% m/m of CaO for 4, 8 and 12% of TS respectively with a minimum contact time of 90 min. The land-application test was done using sludge with 8% TS treated with a quicklime dose of 10% m/m. Nitrogen-based Agronomic Rates (AR) of 0, 1, 5, 10 and 15 were evaluated in the cultivation and production of chayote (Sechium edule). The results with 5 AR showed an estimated total production of 70 kg of the vegetable species over a period of 90 d, which is higher than that reported for the same crop grown without biosolids application

Biomimetic Phosphate-Catalyzed Pictet–Spengler Reaction for the Synthesis of 1,1′-Disubstituted and Spiro-Tetrahydroisoquinoline Alkaloids

Tetrahydroisoquinoline (THIQ) alkaloids are an important group of compounds that exhibit a range of bioactivities. Here, a phosphate buffer-catalyzed Pictet-Spengler reaction (PSR) using unreactive ketone substrates is described. A variety of 1,1'-disubstituted and spiro-tetrahydroisoquinoline alkaloids were readily prepared in one-step and high yields, highlighting the general applicability of this approach. This study features the role of phosphate in the aqueous-based PSR and provides an atom-efficient, sustainable route to new THIQs

Engineering transketolase to accept both unnatural donor and acceptor substrates and produce α‐hydroxyketones

A narrow substrate range is a major limitation in exploiting enzymes more widely as catalysts in synthetic organic chemistry. For enzymes using two substrates, the simultaneous optimisation of both substrate specificities is also required for the rapid expansion of accepted substrates. Transketolase (TK) catalyses the reversible transfer of a C2‐ketol unit from a donor substrate to an aldehyde acceptor and suffers the limitation of narrow substrate scope for industrial applications. Herein, TK from Escherichia coli was engineered to accept both pyruvate, as a novel donor substrate, and unnatural acceptor aldehydes, including propanal, pentanal, hexanal and 3‐formylbenzoic acid (FBA). Twenty single‐mutant variants were first designed and characterised experimentally. Beneficial mutations were then recombined to construct a small library. Screening of this library identified the best variant with a 9.2‐fold improvement in the yield towards pyruvate and propionaldehyde, relative to wild‐type (WT). Pentanal and hexanal were used as acceptors to determine stereoselectivities of the reactions, which were found to be higher than 98% enantiomeric excess (ee) for the S configuration. Three variants were identified to be active for the reaction between pyruvate and 3‐FBA. The best variant was able to convert 47% of substrate into product within 24 h, whereas no conversion was observed for WT. Docking experiments suggested a cooperation between the mutations responsible for donor and acceptor recognition, which would promote the activity towards both the acceptor and donor. The variants obtained have the potential to be used for developing catalytic pathways to a diverse range of high‐value products

Single step syntheses of (1S)-aryl-tetrahydroisoquinolines by norcoclaurine synthases

The 1-aryl-tetrahydroisoquinoline (1-aryl-THIQ) moiety is found in many biologically active molecules. Single enantiomer chemical syntheses are challenging and although some biocatalytic routes have been reported, the substrate scope is limited to certain structural motifs. The enzyme norcoclaurine synthase (NCS), involved in plant alkaloid biosynthesis, has been shown to perform stereoselective Pictet–Spengler reactions between dopamine and several carbonyl substrates. Here, benzaldehydes are explored as substrates and found to be accepted by both wild-type and mutant constructs of NCS. In particular, the variant M97V gives a range of (1 S)-aryl-THIQs in high yields (48–99%) and e.e.s (79–95%). A co-crystallised structure of the M97V variant with an active site reaction intermediate analogue is also obtained with the ligand in a pre-cyclisation conformation, consistent with (1 S)-THIQs formation. Selected THIQs are then used with catechol O-methyltransferases with exceptional regioselectivity. This work demonstrates valuable biocatalytic approaches to a range of (1 S)-THIQs

Metagenomic ene-reductases for the bioreduction of sterically challenging enones

Ene-reductases (ERs) of the Old Yellow Enzyme family catalyse asymmetric reduction of activated alkenes providing chiral products. They have become an important method in the synthetic chemists' toolbox offering a sustainable alternative to metal-catalysed asymmetric reduction. Development of new biocatalytic alkene reduction routes, however needs easy access to novel biocatalysts. A sequence-based functional metagenomic approach was used to identify novel ERs from a drain metagenome. From the ten putative ER enzymes initially identified, eight exhibited activities towards widely accepted mono-cyclic substrates with several of the ERs giving high reaction yields and stereoselectivities. Two highly performing enzymes that displayed excellent co-solvent tolerance were used for the stereoselective reduction of sterically challenging bicyclic enones where the reactions proceeded in high yields, which is unprecedented to date with wild-type ERs. On a preparative enzymatic scale, reductions of Hajos–Parish, Wieland–Miescher derivatives and a tricyclic ketone proceeded with good to excellent yields

Multienzyme One-Pot Cascades Incorporating Methyltransferases for the Strategic Diversification of Tetrahydroisoquinoline Alkaloids

The tetrahydroisoquinoline (THIQ) ring system is present in a large variety of structurally diverse natural products exhibiting a wide range of biological activities. Routes to mimic the biosynthetic pathways to such alkaloids, by building cascade reactions in vitro, represents a successful strategy and can offer better stereoselectivities than traditional synthetic methods. S-Adenosylmethionine (SAM)-dependent methyltransferases are crucial in the biosynthesis and diversification of THIQs; however, their application is often limited in vitro by the high cost of SAM and low substrate scope. In this study, we describe the use of methyltransferases in vitro in multi-enzyme cascades, including for the generation of SAM in situ. Up to seven enzymes were used for the regioselective diversification of natural and non-natural THIQs on an enzymatic preparative scale. Regioselectivites of the methyltransferases were dependent on the group at C-1 and presence of fluorine in the THIQs. An interesting dual activity was also discovered for the catechol methyltransferases used, which were found to be able to regioselectively methylate two different catechols in a single molecule

Phytochemicals as antibiotic alternatives to promote growth and enhance host health

There are heightened concerns globally on emerging drug-resistant superbugs and the lack of new antibiotics for treating human and animal diseases. For the agricultural industry, there is an urgent need to develop strategies to replace antibiotics for food-producing animals, especially poultry and livestock. The 2nd International Symposium on Alternatives to Antibiotics was held at the World Organization for Animal Health in Paris, France, December 12-15, 2016 to discuss recent scientific developments on strategic antibiotic-free management plans, to evaluate regional differences in policies regarding the reduction of antibiotics in animal agriculture and to develop antibiotic alternatives to combat the global increase in antibiotic resistance. More than 270 participants from academia, government research institutions, regulatory agencies, and private animal industries from >25 different countries came together to discuss recent research and promising novel technologies that could provide alternatives to antibiotics for use in animal health and production; assess challenges associated with their commercialization; and devise actionable strategies to facilitate the development of alternatives to antibiotic growth promoters (AGPs) without hampering animal production. The 3-day meeting consisted of four scientific sessions including vaccines, microbial products, phytochemicals, immune-related products, and innovative drugs, chemicals and enzymes, followed by the last session on regulation and funding. Each session was followed by an expert panel discussion that included industry representatives and session speakers. The session on phytochemicals included talks describing recent research achievements, with examples of successful agricultural use of various phytochemicals as antibiotic alternatives and their mode of action in major agricultural animals (poultry, swine and ruminants). Scientists from industry and academia and government research institutes shared their experience in developing and applying potential antibiotic-alternative phytochemicals commercially to reduce AGPs and to develop a sustainable animal production system in the absence of antibiotics.Fil: Lillehoj, Hyun. United States Department of Agriculture. Agricultural Research Service; ArgentinaFil: Liu, Yanhong. University of California; Estados UnidosFil: Calsamiglia, Sergio. Universitat Autònoma de Barcelona; EspañaFil: Fernandez Miyakawa, Mariano Enrique. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Instituto Nacional de Tecnología Agropecuaria. Centro de Investigación en Ciencias Veterinarias y Agronómicas. Instituto de Patobiología; ArgentinaFil: Chi, Fang. Amlan International; Estados UnidosFil: Cravens, Ron L.. Amlan International; Estados UnidosFil: Oh, Sungtaek. United States Department of Agriculture. Agricultural Research Service; ArgentinaFil: Gay, Cyril G.. United States Department of Agriculture. Agricultural Research Service; Argentin