Immobilization of Adenosine Derivatives onto Cellulose Nanocrystals via Click Chemistry for Biocatalysis Applications.

Adenosine triphosphate (ATP) is a central molecule of organisms and is involved in many biological processes. It is also widely used in biocatalytic processes, especially as a substrate and precursor of many cofactors─such as nicotinamide adenine dinucleotide phosphate (NADP(H)), coenzyme A (CoA), and S-adenosylmethionine (SAM). Despite its great scientific interest and pivotal role, its use in industrial processes is impeded by its prohibitory cost. To overcome this limitation, we developed a greener synthesis of adenosine derivatives and efficiently selectively grafted them onto organic nanoparticles. In this study, cellulose nanocrystals were used as a model combined with click chemistry via a copper-catalyzed azide/alkyne cycloaddition reaction (CuAAC). The grafted adenosine triphosphate derivative fully retains its biocatalytic capability, enabling heterobiocatalysis for modern biochemical processes.

Green Synthesis of UV-Reactive Polycarbonates from Levoglucosenone and 5-Hydroxymethyl Furfural.

This study focuses on the synthesis of fully renewable polycarbonates (PCs) starting from cellulose-based platform molecules levoglucosenone (LGO) and 2,5-bis(hydroxymethyl)furan (BHMF). These unique bio-based PCs are obtained through the reaction of a citronellol-containing triol (Triol-citro) derived from LGO, with a dimethyl carbonate derivative of BHMF (BHMF-DC). Solvent-free polymerizations are targeted to minimize waste generation and promote an eco-friendly approach with a favorable environmental factor (E-factor). The choice of metal catalyst during polymerization significantly influences the polymer properties, resulting in high molecular weight (up to 755 kDa) when Na2 CO3 is employed as an inexpensive catalyst. Characterization using nuclear magnetic resonance confirms the successful incorporation of the furan ring and the retention of the terminal double bond of the citronellol pendant chain. Furthermore, under UV irradiation, the presence of both citronellol and furanic moieties induces singular structural changes, triggering the formation of three distinct structures within the polymer network, a phenomenon herein occurs for the first time in this type of polymer. These findings pave the way to new functional materials prepared from renewable monomers with tunable properties.

An expeditive and green chemo-enzymatic route to diester sinapoyl-l-malate analogues: sustainable bioinspired and biosourced UV filters and molecular heaters.

Sinapoyl malate, naturally present in plants, has proved to be an exceptional UV filter and molecular heater for plants. Although there are nowadays industrially relevant sustainable synthetic routes to sinapoyl malate, its incorporation into certain cosmetic formulations, as well as its adsorption on plant leaves, is limited by its hydrophilicity. To overcome these obstacles, it is important to find a way to effectively control the hydrophilic-lipophilic balance of sinapoyl malate to make it readily compatible with the cosmetic formulations and stick on the waxy cuticle of leaves. To this end, herein, we describe a highly regioselective chemo-enzymatic synthesis of sinapoyl malate analogues possessing fatty aliphatic chains of variable length, enabling the lipophilicity of the compounds to be modulated. The potential toxicity (i.e., mutagenicity, carcinogenicity, endocrine disruption, acute and repeated-dose toxicity), bioaccumulation, persistence and biodegradability potential of these new analogues were evaluated in silico, along with the study of their transient absorption spectroscopy, their photostability as well as their photodegradation products.

Unlocking the access to oxidized coenzyme A via a single-step green membrane-based purification.

A new membrane-based strategy to purify oxidized coenzyme A ((CoAS)2) from adenosine triphosphate (ATP), adenosine diphosphate (ADP) and adenosine monophosphate (AMP) has been developed. Commercially available membranes were screened and studied (permeate flux and overall compounds retention) which allowed the identification of one efficient membrane (GK from Suez Water Technologies & Solutions). Different total compounds concentrations solutions were used in the system in order to find the following working conditions: 4 bars with a total compounds solution of 5.19 g L-1. Applying these conditions to a dia-filtration set-up allowed us to reach 68% pure (CoAS)2 in 4.8 diafiltration volumes (DV) and a 95% (CoAS)2 purity can be predicted in 8.5 DV. A comparative study of green metrics-i.e. process mass index (PMI)-of the classic chromatography vs the membrane-based one demonstrated the great advantages of the latter in terms of sustainability. This strategy unlocks the access to the essential and central cofactor that is coenzyme A.

Synthesis and Enzymatic Degradation of Sustainable Levoglucosenone-Derived Copolyesters with Renewable Citronellol Side Chains.

Recently, a renewable five-membered lactone containing citronellol (HBO-citro) was synthesized from levoglucosenone (LGO). A one-pot two-step pathway was then developed to produce a mixture of 5- and 6-membered Lactol-citro molecules (5ML and 6ML, respectively) from HBO-citro. Proton nuclear magnetic resonance (1H NMR) of a mixture of 5ML and 6ML at varying temperatures showed that the chemical shifts of the hydroxyls, as well as the 5ML:6ML ratio, are temperature-dependent. Indeed, a high temperature, such as 65 °C, led to an up-field shielding of the hydroxyl protons as well as a drop in the 5ML:6ML ratio. The monomers 5ML and 6ML were then engaged in polycondensation reactions involving diacyl chlorides. Renewable copolyesters with low glass transition temperatures (as low as -67 °C) and cross-linked citronellol chains were prepared. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan® 50 BG). A higher degradation rate was found for the polymers prepared using Lactol-citro molecules, compared to those obtained by the polycondensation reactions of diacyl chlorides with Triol-citro-a monomer recently obtained by the selective reduction of HBO-citro.

Unprecedented Biodegradable Cellulose-Derived Polyesters with Pendant Citronellol Moieties: From Monomer Synthesis to Enzymatic Degradation.

Levoglucosenone (LGO) is a cellulose-derived molecule that is present commercially on a multi-ton/year scale. Taking advantage of the α,ß-conjugated ketone of LGO, a new citronellol-containing 5-membered lactone (HBO-citro) was synthesized through a one-pot two-step pathway involving oxa-Michael addition and Baeyer-Villiger oxidation. The solvent-free treatment of HBO-citro with NaBH4 at room temperature led to the full reduction of the lactone moiety which gave a novel fully renewable triol monomer having a citronellol side chain (Triol-citro). Noticeably, by simply changing the reducing agent, temperature and reaction duration, the partial reduction of HBO-citro can be achieved to yield a mixture of 5- and 6-membered Lactol-citro molecules. Triol-citro was chosen to prepare functional renewable polyesters having citronellol pendant chains via polycondensation reactions with diacyl chlorides having different chain lengths. Good thermal stability (Td5% up to 170 °C) and low glass transition temperatures (as low as -42 °C) were registered for the polyesters obtained. The polymers were then hydrolyzed using a commercial lipase from Thermomyces lanuginosus (Lipopan® 50 BG) to assess their biodegradability. A higher degradation profile was found for the polyesters prepared using co-monomers (acyl chlorides) having longer chain lengths. This is likely due to the decreased steric hindrance around the ester bonds which allowed enhanced accessibility of the enzyme.

Sustainable Hyperbranched Functional Materials via Green Polymerization of Readily Accessible Levoglucosenone-Derived Monomers.

The homopolymerization in basic conditions of the recently reported bis(γ-lactone), 2H-HBO-HBO, is herein described for the first time. The solvent-free polymerization of this pentafunctional levoglucosenone (LGO) derivative affords fully renewable poly(vinyl-ether lactone) copolymers with a highly hyperbranched structure. This investigation stems from the polycondensation trials between 2H-HBO-HBO and di(methyl carbonate) isosorbide (DCI) that fails to give the anticipated polycarbonates. Such unexpected behavior is ascribed to the higher reactivity of the 2H-HBO-HBO hydroxy groups toward its α,ß-conjugated endocyclic C═C, rather than the DCI methylcarbonate moieties. The different mechanistic scenarios involved in 2H-HBO-HBO homopolymerization are addressed and a possible structure of poly(2H-HBO-HBO) is suggested. Furthermore, the readily accessible (S)-γ-hydroxymethyl-α,ß-butenolide (HBO) is also polymerized for the first time at a relatively large scale, without any prior modification, resulting in a new hyperbranched polymer with an environmental factor (E factor) ≈0. These new HBO-based polymers have a great potential for industrial-scale production due to their interesting properties and easy preparation via a low-cost, green, and efficient process.

Selective Extraction of Sinapic Acid Derivatives from Mustard Seed Meal by Acting on pH: Toward a High Antioxidant Activity Rich Extract.

The aim of this paper is to study the effect of the pH on the extraction of sinapic acid and its derivatives from mustard seed meal. Solutions of acidic pH (pH 2), basic pH (pH 12) and distilled water (uncontrolled pH ~ 4.5) were tested at different percentages of ethanol. The maximum extraction yield for sinapic acid (13.22 µmol/g of dry matter (DM)) was obtained with a buffered aqueous solution at pH 12. For ethyl sinapate, the maximum extraction yield reached 9.81 µmol/g DM with 70% ethanol/buffered aqueous solution at pH 12. The maximum extraction yield of sinapine (15.73 µmol/g DM) was achieved with 70% ethanol/buffered aqueous solution at pH 2. The antioxidant activity of each extract was assessed by DPPH assay; the results indicated that the extracts obtained at pH 12 and at low ethanol percentages (<50%) exhibit a higher antioxidant activity than extracts obtained at acidic conditions. Maximum antioxidant activity was reached at pH 12 with buffer solution (11.37 mg of Trolox Equivalent/g DM), which confirms that sinapic acid-rich fractions exhibit a higher antioxidant activity. Thus, to obtain rich antioxidant extracts, it is suggested to promote the presence of sinapic acid in the extracts.

Grafting Nature-Inspired and Bio-Based Phenolic Esters onto Cellulose Nanocrystals Gives Biomaterials with Photostable Anti-UV Properties.

Invited for this month's cover is the international collaborative work from the Bioresource Processing Research Institute of Australia (BioPRIA)-Monash University and URD Agro-Biotechnologies Industrielles (ABI)-AgroParisTech. The cover image shows how the grafting of Nature-inspired and bio-based phenolic esters on cellulose nanocrystals through click-chemistry provides materials with highly photostable UV-blocking properties. Cover art by David Mendoza. The Full Paper itself is available at 10.1002/cssc.202002017.

Grafting Nature-Inspired and Bio-Based Phenolic Esters onto Cellulose Nanocrystals Gives Biomaterials with Photostable Anti-UV Properties.

New nature-inspired and plant-derived p-hydroxycinnamate esters and p-hydroxycinnamate diesters provide excellent protection against UV radiation when incorporated into a matrix. Herein, an efficient and sustainable pathway is reported to graft these phenolic compounds onto cellulose nanocrystals (CNCs) via click-type copper-catalyzed azide/alkyne cycloaddition (CuAAC) reaction. The successful grafting of the phenolic esters on CNC surface was evidenced by a range of chemical analyses, and the degrees of substitution (DS) of the CNC were found to depend on the structure of the phenolic ester grafted. Moreover, aqueous suspensions of the phenolic ester-grafted CNCs not only strongly absorb in both the UVA and UVB regions, but they also exhibit average to very high photostability. Their wide spectrum UV-absorbing properties and their stability upon exposure to UV are highly influenced by the structure of the phenolic ester, particularly by the extra ester group in p-hydroxycinnamate diesters. These findings demonstrate that cellulose nanocrystals decorated with such plant-derived and nature-inspired phenolic esters are promising sustainable nanomaterials for anti-UV applications.

Sustainable Straightforward Synthesis and Evaluation of the Antioxidant and Antimicrobial Activity of Sinapine and Analogues.

Naturally occurring sinapine was successfully synthesized through a proline-mediated Knoevenagel-Doebner condensation in ethanol. This synthetic process involving biobased syringaldehyde, Meldrum's acid, and choline chloride offers a sustainable alternative to the existing low-yield pathways. This two-step strategy gives access to sinapine in a 52% overall yield and has been implemented in the synthesis of sinapine analogues, using 4-hydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, and vanillin as precursors, giving target molecules with 34-61% overall isolated yields. The purity of synthetic sinapine and its analogues (ca. 95%) was assessed by NMR and high-performance liquid chromatography-mass spectrometry analyses. Furthermore, the antioxidant and antimicrobial activities were assessed, and the potential of this series of molecules was confirmed.

Towards symmetry driven and nature inspired UV filter design.

In plants, sinapate esters offer crucial protection from the deleterious effects of ultraviolet radiation exposure. These esters are a promising foundation for designing UV filters, particularly for the UVA region (400 - 315 nm), where adequate photoprotection is currently lacking. Whilst sinapate esters are highly photostable due to a cis-trans (and vice versa) photoisomerization, the cis-isomer can display increased genotoxicity; an alarming concern for current cinnamate ester-based human sunscreens. To eliminate this potentiality, here we synthesize a sinapate ester with equivalent cis- and trans-isomers. We investigate its photostability through innovative ultrafast spectroscopy on a skin mimic, thus modelling the as close to true environment of sunscreen formulas. These studies are complemented by assessing endocrine disruption activity and antioxidant potential. We contest, from our results, that symmetrically functionalized sinapate esters may show exceptional promise as nature-inspired UV filters in next generation sunscreen formulations.

Application of Acetyl-CoA synthetase from Methanothermobacter thermautotrophicus to non-native substrates.

The substrate selectivity of the Trp416Gly mutant of Methanothermobacter thermautotrophicus acetyl-CoA synthetase (Trp416Gly MT-ACS1) was explored. The goal was to identify its substrate range, particularly for functionalized carboxylic acid substrates that would allow post-synthesis functionalization of CoA thioesters or downstream products using metathesis or Click chemistry. Relative activities were determined by in situ formation of acyl-hydroxamate iron (III) complexes. Trp416Gly MT-ACS1 showed good activities for saturated straight chain carboxylic acids from C2 to C8, for ω-alkenyl straight chain carboxylic acids from C4 to C7 and for ω-alkynyl straight chain carboxylic acids from C5 to C7. Carboxylic acids showing ≥20% conversion in screening reactions were used in preparative conversions that completely consumed the added CoASH.

Corrigendum: Microwave-Assisted Knoevenagel-Doebner Reaction: An Efficient Method for Naturally Occurring Phenolic Acids Synthesis.

[This corrects the article DOI: 10.3389/fchem.2018.00426.].

Microwave-Assisted Knoevenagel-Doebner Reaction: An Efficient Method for Naturally Occurring Phenolic Acids Synthesis.

The common chemical method to synthesize Phenolic Acids (PAs) involves a relatively considerable energy intake. In order to solve this issue, microwave-assisted Knoevenagel-Doebner condensations were developed. Nevertheless, these synthetic procedures prove difficult to reproduce. Herein, we developed and optimized-by using a combination of a Design of Experiment and a standard optimization approach-a reliable procedure that converts naturally occuring p-hydroxybenzaldehydes into the corresponding PAs with conversions of 86-99% and in 85-97% yields.