Enantioselective synthesis of 14-hydroxy-6-oxomorphinans.

The enantioselective synthesis of pharmacologically important 14-hydroxy-6-oxomorphinans is described. 4,5-Desoxynaltrexone and 4,5-desoxynaloxone were prepared using this route and their biological activities against the opioid receptors were measured.

Predictive Molecular Design and Structure-Property Validation of Novel Terpene-Based, Sustainably Sourced Bacterial Biofilm-Resistant Materials.

Presented in this work is the use of a molecular descriptor, termed the α parameter, to aid in the design of a series of novel, terpene-based, and sustainable polymers that were resistant to biofilm formation by the model bacterial pathogen . To achieve this, the potential of a range of recently reported, terpene-derived monomers to deliver biofilm resistance when polymerized was both predicted and ranked by the application of the α parameter to key features in their molecular structures. These monomers were derived from commercially available terpenes (, α-pinene, β-pinene, and carvone), and the prediction of the biofilm resistance properties of the resultant novel (meth)acrylate polymers was confirmed using a combination of high-throughput polymerization screening (in a microarray format) and testing.

High Yielding Continuous-Flow Synthesis of Norketamine.

A new continuous-flow process is presented for synthesis of the pharmaceutical intermediate norketamine (). Our approach has been to take the well-established and industrially applied batch synthetic route to this promising antidepressant precursor and convert it to a telescoped multi-stage continuous-flow platform. This involves the α-bromination of a ketone, an imination/rearrangement sequence with liquid ammonia, and a thermally induced α-iminol rearrangement.

Practical genetic control strategies for industrial bioprocesses.

Optimization of metabolism to maximize production of bio-based chemicals must consistently balance cellular resources for biocatalyst growth and desired compound synthesis. This mini-review discusses synthetic biology strategies for dynamically controlling expression of genes to enable dual-phase fermentations in which growth and production are separated into dedicated phases. Emphasis is placed on practical examples which can be reliably scaled to commercial production with the current state of technology.

Functionalisable Epoxy-rich Electrospun Fibres Based on Renewable Terpene for Multi-Purpose Applications.

New bio-based polymers capable of either outperforming fossil-based alternatives or possessing new properties and functionalities are of relevant interest in the framework of the circular economy. In this work, a novel bio-based polycarvone acrylate di-epoxide (PCADE) was used as an additive in a one-step straightforward electrospinning process to endow the fibres with functionalisable epoxy groups at their surface. To demonstrate the feasibility of the approach, poly(vinylidene fluoride) (PVDF) fibres loaded with different amounts of PCADE were prepared.

Development of Conductive Gelatine-Methacrylate Inks for Two-Photon Polymerisation.

Conductive hydrogel-based materials are attracting considerable interest for bioelectronic applications due to their ability to act as more compatible soft interfaces between biological and electrical systems. Despite significant advances that are being achieved in the manufacture of hydrogels, precise control over the topographies and architectures remains challenging. In this work, we present for the first time a strategy to manufacture structures with resolutions in the micro-/nanoscale based on hydrogels with enhanced electrical properties.

Terpene polyacrylate TPA5 shows favorable molecular hydrodynamic properties as a potential bioinspired archaeological wood consolidant.

There is currently a pressing need for the development of novel bioinspired consolidants for waterlogged, archaeological wood. Bioinspired materials possess many advantages, such as biocompatibility and sustainability, which makes them ideal to use in this capacity. Based on this, a polyhydroxylated monomer was synthesised from α-pinene, a sustainable terpene feedstock derived from pine trees, and used to prepare a low molar mass polymer TPA5 through free radical polymerisation.

General Method for the Asymmetric Synthesis of N-H Sulfoximines via C-S Bond Formation.

A versatile method for the synthesis of enantioenriched N-H sulfoximines is reported. The approach stems from the organomagnesium-mediated ring opening of novel cyclic sulfonimidate templates. The reactions proceed in high yield and with excellent stereofidelity with alkyl, aryl, and heteroaryl Grignard reagents.

Sulfonimidates: Useful Synthetic Intermediates for Sulfoximine Synthesis via C-S Bond Formation.

Medicinally relevant sulfoximines are accessed from C-S coupling of sulfonimidates and commercially available organomagnesium reagents. Sulfonimidates are conveniently synthesized by oxidative alkoxylation of readily available sulfinamides. This constitutes a general C-S coupling approach for the synthesis of sulfoximines.

Biomimetic Approaches Towards The Synthesis of Complex Dimeric Natural Products.

We present a selection of elegant and diverse biomimetic syntheses of complex natural product dimers. The dimerisation pathways discussed encompass the most prevalent strategies, including: Diels-Alder, Aldol, Mannich, conjugate addition, oxidative, radical and photochemical approaches; each underpinned through rational biosynthetic speculation.

Formal synthesis of kingianin A based upon a novel electrochemically-induced radical cation Diels-Alder reaction.

The application of electrochemical reactions in natural product synthesis has burgeoned in recent years. We herein report a formal synthesis of the complex and dimeric natural product kingianin A, which employs an electrochemically-mediated radical cation Diels-Alder cycloaddition as the key step.

Metabolic engineering for production of biorenewable fuels and chemicals: contributions of synthetic biology.

Production of fuels and chemicals through microbial fermentation of plant material is a desirable alternative to petrochemical-based production. Fermentative production of biorenewable fuels and chemicals requires the engineering of biocatalysts that can quickly and efficiently convert sugars to target products at a cost that is competitive with existing petrochemical-based processes. It is also important that biocatalysts be robust to extreme fermentation conditions, biomass-derived inhibitors, and their target products.

Metabolic evolution of energy-conserving pathways for succinate production in Escherichia coli.

During metabolic evolution to improve succinate production in Escherichia coli strains, significant changes in cellular metabolism were acquired that increased energy efficiency in two respects. The energy-conserving phosphoenolpyruvate (PEP) carboxykinase (pck), which normally functions in the reverse direction (gluconeogenesis; glucose repressed) during the oxidative metabolism of organic acids, evolved to become the major carboxylation pathway for succinate production. Both PCK enzyme activity and gene expression levels increased significantly in two stages because of several mutations during the metabolic evolution process.