Temporal patterns of fucoxanthin in four species of European marine brown macroalgae.

Brown seaweeds are a rich source of carotenoids, particularly fucoxanthin, which has a wide range of potential health applications. Fucoxanthin fluctuates within and among seaweeds over time, frustrating efforts to utilise this resource. Thus, we require comprehensive analyses of long- and short-term concentrations across species in field conditions. Here, we used High Performance Liquid Chromatography to compare fucoxanthin content in four brown macroalgae, Ascophyllum nodosum, Fucus serratus, Fucus vesiculosus and Saccharina latissima, monthly for 1 year. F. serratus and F. vesiculosus had significantly higher fucoxanthin content (mg/g), which was highest in Spring (0.39 ± 0.04) and Autumn (0.45 ± 0.04) [mean (± SE)]. Two species, A. nodosum and F. serratus, were collected monthly at the same location for a further two non-consecutive years. For both A. nodosum and F. serratus, a significant interaction effect of seasons and years was identified, highlighting that there is variation in fucoxanthin content among and within species over time. We also show that fucoxanthin content differs significantly among months even within seasons. Therefore, it is not sufficient to assess fucoxanthin in single months to represent seasonality. We discuss how weather, nutrients and reproduction may have driven the seasonal variation, and reveal patterns of fucoxanthin concentration that can provide information concerning its availability for many important medical functions.

Ruthenium ion catalysed C-C bond activation in lignin model compounds - towards lignin depolymerisation.

Lignin is the most abundant renewable feedstock to produce aromatic chemicals, however its depolymerisation involves the breaking of several C-O and C-C inter-unit linkages that connect smaller aromatic units that are present in lignin. Several strategies have been reported for the cleavage of the C-O inter-unit linkages in lignin. However, till today, only a few methodologies have been reported for the effective breaking or the conversion of the recalcitrant C-C inter unit linkages in lignin. Here we report the ruthenium ion catalysed oxidative methodology as an effective system to activate or convert the most recalcitrant inter unit linkages such as ß-5 and 5-5' present in lignin. Initially, we used biphenyl as a model compound to study the effectiveness of the RICO methodology to activate the 5-5' C-C linkage. After 4 h reaction at 22 °C, we achieved a 30% conversion with 75% selectivity towards benzoic acid and phenyl glyoxal as the minor product. To the best of our knowledge this is the first ever oxidative activation of the C-C bond that connects the two phenyl rings in biphenyl. DFT calculation revealed that the RuO4 forms a [3 + 2] adduct with one of the aromatic C-C bonds resulting in the opening of the phenyl ring. Biphenyl conversion could be increased by increasing the amount of oxidant; however, this is accompanied by a reduction in the carbon balance because of the formation of CO2 and other unknown products. We extended this RICO methodology for the oxidative depolymerisation of lignin model hexamer containing ß-5, 5-5' and ß-O-4 linkages. Qualitative and quantitative analyses of the reaction mixture were done using 1H, 13C NMR spectroscopy methods along with GC-MS and Gel Permeation Chromatographic (GPC) methods. Advanced 2D NMR spectroscopic methods such as HSQC, HMBC and 31P NMR spectroscopy after phosphitylation of the mixture were employed to quantitatively analyse the conversion of the ß-5, 5-5' and ß-O-4 linkages and to identify the products. After 30 min, >90% of the 5-5' and linkages and >80% of the ß-5' are converted with this methodology. This is the first report on the conversion of the 5-5' linkage in lignin model hexamer.

Toward the Photocatalytic Valorization of Lignin: Conversion of a Model Lignin Hexamer with Multiple Functionalities.

The valorization of biomass via photocatalysis is an area of expanding research with advances in new technologies and materials with a view toward enhanced sustainability being reported. A significant challenge within this field, however, is understanding the impact photocatalysis has on more recalcitrant compounds present in biomass, such as lignin. Moreover, the current state of lignin model compound research is still largely focused on the breakdown of small models containing typically only one linkage. Described herein is the use of TiO2-mediated photocatalysis for the degradation of a representative hexameric lignin model compound which contains multiple linkages (e.g., 5-5', ß-5, and ß-O-4). The results revealed that while cleavage of the ß-5 and ß-O-4 occurred, the 5-5' appeared to remain intact within the identified reaction intermediates. To understand some of the more fundamental questions, a dimeric compound with a biphenyl linkage was synthesized and studied under photocatalytic conditions. The proposal of intermediates and pathways of degradation based on the studies conducted is presented and discussed herein.

Photocatalytic Reforming of Biomass: What Role Will the Technology Play in Future Energy Systems.

Photocatalytic reforming of biomass has emerged as an area of significant interest within the last decade. The number of papers published in the literature has been steadily increasing with keywords such as 'hydrogen' and 'visible' becoming prominent research topics. There are likely two primary drivers behind this, the first of which is that biomass represents a more sustainable photocatalytic feedstock for reforming to value-added products and energy. The second is the transition towards achieving net zero emission targets, which has increased focus on the development of technologies that could play a role in future energy systems. Therefore, this review provides a perspective on not only the current state of the research but also a future outlook on the potential roadmap for photocatalytic reforming of biomass. Producing energy via photocatalytic biomass reforming is very desirable due to the ambient operating conditions and potential to utilise renewable energy (e.g., solar) with a wide variety of biomass resources. As both interest and development within this field continues to grow, however, there are challenges being identified that are paramount to further advancement. In reviewing both the literature and trajectory of the field, research priorities can be identified and utilised to facilitate fundamental research alongside whole systems evaluation. Moreover, this would underpin the enhancement of photocatalytic technology with a view towards improving the technology readiness level and promoting engagement between academia and industry.

Polyphenols from Brown Seaweeds as a Potential Antimicrobial Agent in Animal Feeds.

Seaweeds offer a natural source of antimicrobials that may help curb antibiotic resistance in livestock. The antibacterial activity of phlorotannin extracts isolated from two brown seaweeds Ascophyllum nodosum and Fucus serratus was tested. The mechanism of action of phlorotannin extracts against Escherichia coli O157, Salmonella agona, and Streptococcus suis was elucidated by observing cell membrane permeability and intracellular adenosine triphosphate (ATP). The two extracts were effective at killing three foodborne pathogens without negatively affecting the pig intestinal cells. A. nodosum minimum inhibitory concentration (MIC) range for the different pathogens was between 1.56 and 0.78 mg/mL, whereas F. serratus was 3.13 mg/mL for all pathogens tested. A. nodosum was found to be much more potent compared to F. serratus. The difference in potency in the seaweeds may be a result of the phlorotannins' structural linkages. The antimicrobial properties of the seaweed extracts tested may provide alternative and complementary treatments to antibiotics and zinc oxide in animal feeds. The seasonal screening was performed on both species to assess the availability of phenolics throughout the year using two quantification methods, the Folin-Ciocalteu (FC) assay and quantitative nuclear magnetic resonance (NMR). The variation between the methods highlights the challenges involved in the quantification of complex phenolic structures. However, both methods show that the phenolics are subject to seasonal variation, which may prove problematic to the animal feed industry.

A critical review of analytical methods used for the chemical characterisation and quantification of phlorotannin compounds in brown seaweeds.

INTRODUCTION: Phlorotannins, the phenolic compounds found in brown seaweeds, are a unique and diverse class of compounds showing a huge potential for food and pharmaceutical applications. OBJECTIVE: This review will give an account of the colorimetric assays used and a discussion of their quantitative and qualitative analytical shortcomings. It will also discuss other more complex and modern analytical chemistry methods that are currently being developed to study phlorotannins. The purpose of this review is to increase awareness of these bioactive compounds and promote further development of robust analytical methods for use in biology, food science, pharmacology and biomedical and cosmeceutical sciences. RESULTS: Whilst the biological activity and huge commercial potential of the phlorotannins has been widely reported throughout the literature, the chemical structures and reactivity of these compounds is still not well understood. The phlorotannin content of seaweed is usually characterised using colorimetric assays. However, although these methods give a reasonable overall estimation of the total phenolic content, they lack precision and specificity. CONCLUSION: This review highlights the strengths and weaknesses of commonly used colorimetric assays. Novel techniques are highlighted using more selective chemistry to identify this class of compounds.

A chemoenzymatic synthesis of 5a-carba-α-D-mannose-6-phosphate.

An efficient chemical synthesis of 5a-carba-α-D-mannose and its enzymatic elaboration to 5a-carba-α-D-mannose-6-phosphate, using yeast hexokinase, is described.

Dioxygenase-catalysed oxidation of disubstituted benzene substrates: benzylic monohydroxylation versus aryl cis-dihydroxylation and the meta effect.

Biotransformations of a series of ortho-, meta- and para-substituted ethylbenzene and propylbenzene substrates have been carried out, using Pseudomonas putida UV4, a source of toluene dioxygenase (TDO). The ortho- and para-substituted alkylbenzene substrates yielded, exclusively, the corresponding enantiopure cis-dihydrodiols of the same absolute configuration. However, the meta isomers, generally, gave benzylic alcohol bioproducts, in addition to the cis-dihydrodiols (the meta effect). The benzylic alcohols were of identical (R) absolute configuration but enantiomeric excess values were variable. The similar (2R) absolute configurations of the cis-dihydrodiols are consistent with both the ethyl and propyl groups having dominant stereodirecting effects over the other substituents. The model used earlier, to predict the regio- and stereo-chemistry of cis-dihydrodiol bioproducts derived from substituted benzene substrates has been refined, to take account of non-symmetric substituents like ethyl or propyl groups. The formation of benzylic hydroxylation products, from meta-substituted benzene substrates, without further cis-dihydroxylation to yield triols provides a further example of the meta effect during toluene dioxygenase-catalysed oxidations.

Biotransformation of substituted pyridines with dioxygenase-containing microorganisms.

A series of 2-, 3- and 4-substituted pyridines was metabolised using the mutant soil bacterium Pseudomonas putida UV4 which contains a toluene dioxygenase (TDO) enzyme. The regioselectivity of the biotransformation in each case was determined by the position of the substituent. 4-Alkylpyridines were hydroxylated exclusively on the ring to give the corresponding 4-substituted 3-hydroxypyridines, while 3-alkylpyridines were hydroxylated stereoselectively on C-1 of the alkyl group with no evidence of ring hydroxylation. 2-Alkylpyridines gave both ring and side-chain hydroxylation products. Choro- and bromo-substituted pyridines, and pyridine itself, while being poor substrates for P. putida UV4, were converted to some extent to the corresponding 3-hydroxypyridines. These unoptimised biotransformations are rare examples of the direct enzyme-catalysed oxidation of pyridine rings and provide a novel synthetic method for the preparation of substituted pyridinols. Evidence for the involvement of the same TDO enzyme in both ring and side-chain hydroxylation pathways was obtained using a recombinant strain of Escherichia coli (pKST11) containing a cloned gene for TDO. The observed stereoselectivity of the side-chain hydroxylation process in P. putida UV4 was complicated by the action of an alcohol dehydrogenase enzyme in the organism which slowly leads to epimerisation of the initial (R)-alcohol bioproducts by dehydrogenation to the corresponding ketones followed by stereoselective reduction to the (S)-alcohols.

Selective opening of ring C in the morphine skeleton by an unexpected cleavage of the C5-C6 bond in cycloadducts of thebaine and acyl nitroso compounds.

[reaction: see text] Acyl nitroso cycloadducts of the alkaloid thebaine undergo an unexpected cleavage of the C5-C6 bond when treated with 2 equiv of samarium(II) iodide in THF to give novel hexahydrobenzazocine products. A proposed mechanism for the transformation involves rearrangement of the initial radical anion.