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Background: Nowadays, pest infestation and resistance have appeared as a consequence of repeated and extensive use of pesticides. Thus, development of new effective pesticide candidates in crop protection is highly desirable. Herein, a series of new piperine derivatives containing oxime ester scaffolds were regioselectively and stereoselectively prepared as pesticidal agents., Results: Steric configurations of compounds 2, 5z and 13e were definitively determined by single-crystal X-ray diffraction. Against Tetranychus cinnabarinus, notably, compounds 5f [median lethal concentration (LC 50 ) = 0.14 mg mL -1 ] and 5v (LC 50  = 0.13 mg mL -1 ) showed >107-fold greater acaricidal activity than piperine (LC 50  = 15.02 mg mL -1 ), which were comparable to the commercial acaricide spirodiclofen. Against Aphis citricola, compound 5d (LD 50  = 19.12 ng aphid -1 ) exhibited 6.1-fold more potent aphicidal activity than piperine (LD 50  = 116.06 ng aphid -1 ). Additionally, through scanning electron microscopy, the toxicology study suggested that the acaricidal activity of piperine derivatives may be related to damage of the cuticle layer crest of T. cinnabarinus., Conclusion: The structure-activity relationships suggested that 3,4-dioxymethylene of piperine was crucial for its acaricidal activity; and introduction of a certain length of aliphatic chain at the C-2 position was beneficial to the aphicidal and acaricidal activities. Compounds 5f and 5v are potential leads for further structural modification as acaricidal agents. © 2023 Society of Chemical Industry., (© 2023 Society of Chemical Industry.)

Kinetic studies of the reaction of ethyl glycolate HOCH 2 C(O)OCH 2 CH 3 with OH radicals (k OH ) and Cl atoms (k Cl ) have been conducted by the relative method using a glass atmospheric reactor by "in situ" Fourier Transform Infrared (FTIR) and Gas Chromatography equipped with flame ionization detection by Solid Phase Micro Extraction (GC-FID/SPME) at room temperature and atmospheric pressure. The following relative rate coefficients were determined using several reference compounds and two different techniques: k EG +   OH-FTIR = (4.36 ± 1.21) × 10 -12 ; k EG +   OH-GC-FID = (3.90 ± 0.74) × 10 -12 ; and k EG +   Cl-GC-FID = (6.40 ± 0.72) × 10 -11 all values in units of cm 3 .molecule -1 .s -1 . Complementary product studies were performed under comparable conditions to the kinetic tests, in order to identify the reaction products and to postulate their tropospheric oxidation mechanisms. The reaction of OH radicals and Cl atoms with ethyl glycolate initiates via H-atom abstraction from alkyl groups of the molecule. Formic acid was positively identified as a reaction product by FTIR. On the other hand, formaldehyde, acetaldehyde, glycolic acid; and formic acid were identified by the GC-MS technique. The Structure-Activity Relationship, (SAR) calculations were also implemented to estimate the more favorable reaction pathways and compare them with the products identified. Tropospheric lifetimes of τ OH  = 34 h and τ Cl  = 5.5 days were estimated to determine how these investigated reactions might affect the air quality. In this sense, average ozone production of [O 3 ] = 0.75 and a Photochemical Ozone Creation Potential, POCP, of 38 were calculated for the hydroxyl ester studied., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Rapid cellular uptake of synthetic molecules remains a challenge, and the motif frequently employed to generate prodrugs, succinic ester, unfortunately lowers the efficacy of the desired drugs due to their slow ester hydrolysis and low cell entry. Here we show that succinic ester-containing diglycine drastically boosts the cellular uptake of supramolecular assemblies or prodrugs. Specifically, autohydrolysis of the diglycine-activated succinic esters turns the nanofibers of the conjugates of succinic ester and self-assembling motif into nanoparticles for fast cellular uptake. The autohydrolysis of diglycine-activated succinic esters and drug conjugates also restores the efficacy of the drugs. 2D nuclear magnetic resonance (NMR) suggests that a "U-turn" of diglycine favors intramolecular hydrolysis of diglycine-activated succinic esters to promote autohydrolysis. As an example of rapid autohydrolysis of diglycine-activated succinic esters for instant cellular uptake, this work illustrates a nonenzymatic bond cleavage approach to develop effective therapeutics for intracellular targeting., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Efficient routes for the preparation of functional self-healing hydrogels from functional polymers are needed. In this study, we developed a strategy to effectively produce a vanillin-modified poly(vinyl alcohol) (PVA-vanillin) through the Hantzsch reaction. This polymer was cross-linked with a phenylboronic acid-containing polymer (PB) that was also prepared using the Hantzsch reaction to fabricate a hydrogel through borate ester linkages under mild conditions (25 °C, pH ∼ 7.4). This hydrogel had excellent antioxidant abilities due to the 1,4-dihydropyridine (DHP) rings and the vanillin moieties in the hydrogel structures; it was also self-healable and injectable owing to the dynamic borate ester linkages. Furthermore, the antioxidant self-healing hydrogel had low cytotoxicity and exhibited favorable safety in animal experiments, indicating its potential as a safe implantable cell or drug carrier. This study developed a method for preparing functional polymers and related self-healing hydrogels in a facile manner; it demonstrated the value of the Hantzsch reaction in exploiting antioxidant self-healing hydrogels for biomedical applications, which may provide insight into the design of other functional self-healing hydrogels through different multicomponent reactions.

Background: Poor mechanical and water barrier properties of starch-based films severely restrict their applications as packaging materials. In this study, glycerol was combined with various small molecular esters (SMEs) with different molecular structures to plasticize high-content starch/poly(butylene adipate-co-terephthalate) (80/20, w/w) films (SPFs) prepared by extrusion blowing. The effects of co-plasticization on the physicochemical properties and film-forming mechanism of SPFs were investigated., Results: The addition of glycerides to SPFs reduced intermolecular interaction, increased molecular chain mobility, and decreased glass transition, melting temperatures, and crystallinity. Mechanical and water barrier properties of SPFs were improved significantly with the co-plasticization of glycerol and SMEs. The incorporation of triacetate glyceride increased tensile strength of SPFs by 54% and the water contact angle by up to 95°. The SPF with diacetate glyceride exhibited the minimum water vapor permeability, which decreased by 39%., Conclusion: The levels of hydrophilic/hydrophobic groups in SMEs and their molecular weights were essential for the plasticizing effects. Glycerides tended to infiltrate into starch for effective plasticization compared with citrates. The combination of glycerol and glycerides had better plasticizing effects on starch. © 2023 Society of Chemical Industry., (© 2023 Society of Chemical Industry.)

The development of catalyst-free ester-based covalent adaptable networks (CANs) provides a new approach to achieve milder reaction conditions to reprocess thermoset resins. Despite recent advances, however, accelerating network rearrangements requires the introduction of hydroxyl groups into the network. In this study, disulfide bonds are introduced into the CANs to add new kinetically facile pathways to accelerate network rearrangement. Kinetic experiments using small molecule models of the CANs show that the presence of the disulfide bonds can accelerate transesterification. These insights are applied to synthesize new kinds of poly(β-hydrazide disulfide esters) (PSHEs) using thioctic acyl hydrazine (TAH) as a precursor for ring-opening polymerization with the hydroxyl-free multifunctional acrylates. The PSHE CANs have lower relaxation times (505-652 s) than the polymer containing only β-hydrazide esters (2903 s). The ring-opening polymerization of TAH improves the crosslinking density, heating resistance deformation temperature, and UV shielding performance of the PSHEs. Thus, this work provides a practical strategy to reduce the reprocessing temperatures of CANs., (© 2023 Wiley-VCH GmbH.)

The first total synthesis of icosalide A, an antibacterial depsipeptide that is unique in that it contains two lipophilic beta-hydroxy acids, has been achieved by following Fmoc solid-phase peptide synthesis in combination with solution-phase synthesis. The ambiguity in the absolute stereochemistry of icosalide A has been resolved by synthesizing the reported structures and other relevant diastereomers of icosalides and comparing their NMR data. NMR-based structure elucidation of icosalide A revealed a well-folded structure with cross-strand hydrogen bonds similar to the anti-parallel beta-sheet conformation in peptides and displayed a synergistic juxtaposition of the aliphatic sidechains. 12 analogues of icosalide A were synthesized by varying the constituent lipophilic beta-hydroxy acid residues, and their biological activities against Bacillus thuringiensis and Paenibacillus dendritiformis were explored. Most of these icosalide analogues showed an MIC of 12.5 μg mL -1 against both bacteria. Swarming inhibition by icosalides was least in B. thuringiensis (8.3%) compared to that in P. dendritiformis (33%). Furthermore, this is the first report of icosalides showing assured inhibitory action (MIC between 2 and 10 μg mL -1 ) against the active stage of Mycobacterium tuberculosis and cancer cell lines such as HeLa and ThP1. This study could help optimize icosalides for anti-TB, antibacterial, and anti-cancer activities.

The use of lithio tris(methylthio)methane as a hydroxy/thio/amino carbonyl anion equivalent in the synthesis of α-amino acids is reported. Addition of the reagent to nonracemic sulfinimines furnished the α-sulfinamido trithioformates in excellent diastereoselectivity. Unmasking the trithioformates to diverse functionalities, such as α-amino acid thioesters, esters, anilides, amides, and di/tri peptides, without epimerization of chiral centers was accomplished.

Stabilization of a peptide conformation via stapling strategy may be realized by the reversible or more often irreversible connection of side chains being in mutually appropriate geometry. An incorporation of phenylboronic acid and sugar residues (fructonic or galacturonic acid), attached to two lysine side chains via amide bonds and separated by 2, 3, or 6 other residues in the C-terminal fragment of RNase A introduces the intramolecular interaction stabilizing the α-helical organization. The boronate ester stapling is stabilized in mild basic conditions and may be switched off by acidification leading to unfolded organization of the peptide chain. We investigated the possibility of using switchable stapling by mass spectrometry, NMR and UV-CD spectroscopies, and DFT calculations., (© 2023 Wiley-VCH GmbH.)

An operationally simple Knoevenagel condensation/asymmetric epoxidation/domino ring-opening esterification (DROE) approach has been disclosed to successfully access a good variety of ( R )- and ( S )-α-arylglycine esters from commercially available aldehydes, phenylsulfonyl acetonitrile, cumyl hydroperoxide, anilines, and readily available Cinchona alkaloid-based catalysts using a single solvent and reaction vessel. DFT calculations performed on the key asymmetric epoxidation showed the importance of cooperative H-bonding interactions in affecting the stereocontrol.

In this account, we further describe our already developed N-sp 2 hybrid guanidinium as an efficient phase-transfer catalyst and ion pair catalysis based on N-sp 2 hybrid pentanidinium and its application in some new reactions. The sp 3 hybrid quaternary ammonium salt has a tetrahedral structure, which means that three sides of it can be effectively steric, allowing the remaining side to be close to the substrate. However, the sp 2 hybrid ammonium salt allows the substrate to form ion pairs from both directions respectively, so it is a greater challenge to control the stereoselectivity of the reaction. Van der Waals forces, such as hydrogen bonds and π - π ${\pi -\pi }$ interactions, have been used to make electrophiles approach from a certain direction, leading to a higher enantioselectivity. Based on the above idea, we designed an N-sp 2 hybrid phase-transfer catalyst, pentanidinium. Pentanidinium has five conjugated nitrogen atoms, one of which has a formal positive charge, which is necessary for it to become an ion pair catalyst. We have confirmed that pentanidinium can catalyze α-hydroxylation of 3-substituted-2-oxindoles, Michael addition of 3-alkyloxindoles with vinyl sulfone, and alkylation reactions of sulfenate anions and dihydrocoumarins, desymmetrization of pro-chiral sulfinate to afford enantioenriched sulfinate esters. Pentanidinium with side chain structure changes can also be catalyzed efficiently with enantioconvergent halogenophilic nucleophilic substitution, including azidation and thioesterification. In the reaction catalyzed by pentanidinium, it always attracts us with the advantages of low catalytic load and good enantioselectivity., (© 2023 The Chemical Society of Japan & Wiley-VCH GmbH.)

Four new ferulic acid sucrose esters, β -D-(1- O -acetyl-6- O - trans -feruloyl)fructofuranosyl- a -D-2',6'- O -diacetylglucopyranoside ( 1 ), β -D-(1- O -acetyl-6- O - trans -feruloyl)fructofuranosyl- a -D-2',4'- O -diacetylglucopyranoside ( 2 ), β -D-(6- O - trans -feruloyl)fructofuranosyl- a -D-2',4',6'- O -triacetylglucopyranoside ( 3 ), β -D-(1- O -acetyl-6- O - trans -feruloyl)fructofuranosyl- a -D-4',6'- O -diacetylglucopyranoside ( 4 ), together with four known phenylpropanoids ( 5 - 8 ) were isolated from the rhizome of Sparganium stoloniferum (Graebn.) Buch.-Ham. ex Juz. Their structures were elucidated by chemical evidence and spectral analysis. Compounds 1-8 exhibited obvious inhibitory effects on ADP-induced platelet aggregation.

Few studies have been performed on allenyl monofluorides, especially on aryl-substituted frames, due to concerns about their stability. Here we report a copper-catalyzed regioselective synthesis of such structures with inexpensive and accessible aryl boronic esters under mild conditions. Arylated allenyl monofluorides were stable enough to be isolated and easily converted to various other fluorine-containing blueprints. Preliminary asymmetric attempts demonstrate that the reaction could proceed via a selective β-fluorine elimination process.

Boronate esters formed by reaction of an oligonucleotide carrying a 5'-boronic acid moiety with the 3'-terminal cis-diol of another have been shown previously to assist assembly of fragmented DNAzymes. Here we demonstrate that boronate esters replacing the natural phosphodiester linkage at selected sites of two functional RNAs, the hairpin ribozyme and the Mango aptamer, allow assembly of functional structures. The hairpin ribozyme, a small naturally occurring RNA that supports the reversible cleavage of appropriate RNA substrates, is very sensitive to fragmentation. Splitting the ribozyme at four different sites led to a significant decrease or even loss of cleavage and ligation activity. Ribozymes assembled from fragments capable of boronate ester formation showed restoration of cleavage activity in some but not all cases, dependent on the split site. Ligation proved to be more challenging, no supportive effect of the boronate ester was observed. Split variants of the Mango aptamer also showed a dramatic loss of functionality, which however, was restored when 5'-boronic acid modified fragments were used for assembly. These studies show for the first time that boronate esters as internucleoside linkages can act as surrogates of natural phosphodiesters in functional RNA molecules., (© 2023 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Cholinesterases (ChEs) display a non-michaelian behavior with positively charged substrates. In the steady-state rate equation, the b factor describes this behavior: if b > 1 there is substrate activation, if b < 1 there is substrate inhibition. The mechanistic significance of the b factor was investigated to determine whether this behavior depends on acylation, deacylation or on both steps. Kinetics of human acetyl- (AChE) and butyryl-cholinesterase (BChE) were performed under steady-state conditions and using a time-course of complete substrate hydrolysis. For the hydrolysis of short acyl(thio)esters, where acylation and deacylation are partly rate-limiting, steady-state kinetic analysis could not decide which step determines b . However, the study of the hydrolysis of an arylacylamide, 3-(acetamido)-N,N,N-trimethylanilinium (ATMA), where acetylation is rate-limiting, showed that b depends on the acylation step. The magnitude of b and opposite b values between AChE and BChE for the hydrolysis of acetyl(thio)- versus benzoyl-(thio) esters, then indicated that the productive adjustment of substrates in the active center at high concentration depends on motions of both the Ω and the acyl-binding loops. Benzoylcholine was shown to be a poor substrate of AChE, and steady-state kinetics showed a sudden inhibition at high concentration, likely due to the non-dissociation of hydrolysis products. The poor catalytic hydrolysis of this bulky ester by AChE illustrates the importance of the fine adjustment of substrate acyl moiety in the acyl-binding pocket. Molecular modeling and QM/MM simulations should definitively provide evidence for this statement.

Phenolipids such as hydroxytyrosol-SCFA acyl esters (HTy-SEs) and tyrosol-SCFA acyl esters (TYr-SEs) with various alkyl chains lengths (C1-C4) and different isomers (branched-chain and straight-chain) were successfully synthesized. All esters were hydrolyzed by pancreatic lipase to produce polyphenols (HTy and TYr) and SCFAs (iso-butyric acid, acetic acid, propionic acid, and n-butyric acid). Moreover, HTy-SEs (and TYr-SEs) could also be hydrolyzed to free HTy (and TYr) and SCFAs by gut microbiota and Lactobacillus from mice feces. Especially, the hydrolysis rates showed positive correlation with the carbon skeleton length, and the hydrolysis degree (DH) of ester with a branched-chain fatty acid was weaker than that of ester with a straight-chain fatty acid. Besides, the DH values of TYr -SEs were significantly higher than those of HTy-SEs. Therefore, through regulating the structures of polyphenols, carbon skeleton lengths, and isomers, controlled-release of polyphenols and SCFAs from phenolipids will be easily achieved.

A detailed theoretical mechanistic investigation on the dynamic kinetic resolution of N-protected amino acid esters using phase-transfer catalysts is described. Semiautomatic exhaustive conformation search of transition state (TS)-like structures were carried out using the ConFinder program and the pseudo-TS conformational search (PTSCS) method. This conformational search method successfully provided reasonable TS structures for determining the stereoselectivity in the asymmetric base hydrolysis of hexafluoroisopropyl (HFIP) esters as well as the racemization mechanism. Furthermore, the independent gradient model (IGM) analysis of the TS structures suggested that the H-bonding interactions with the oxyanion hole and π-stacking interactions are the common important features of the proposed TS structures that determine the stereoselectivity.

Novel boronyl borinic ester I was generated by quenching the B 2 pin 2 / sec BuLi-ate complex with trifluoroacetic acid anhydride (TFAA) via ring-opening in the 1,3,2-dioxaborolane moiety on ate-boron. Detailed NMR studies of the B 2 pin 2 / sec BuLi-ate complex in solution and in solid state allowed us to assume its oligomeric nature in solids with only ate-boron involved in the oligomerization process. The O-trifluoroacetyl pinacolate residue on borinic ester I initially formed on quenching with TFAA undergoes an unusual intramolecular transesterification with the carbonyl group of trifluoroacetyl forming othroester moiety in a few hours at r. t. to give boronyl borinic ester II. A solution of these reagents I/II was proved to be efficient for borylation of (2-fluoroallyl)pyridinium salts that are highly base sensitive., (© 2023 Wiley-VCH GmbH.)

Twenty-four new phenylpropanoid esters of sucrose, phanerosides A-X ( 1 - 24 ), were isolated from an EtOH extract of the rattans of Phanera championii Benth. (Fabaceae). Their structures were elucidated on the basis of comprehensive spectroscopic data analysis. A wide range of structural analogues were presented due to the different numbers and positions of acetyl substituents and the structures of phenylpropanoid moieties. Phenylpropanoid esters of sucrose were isolated from the Fabaceae family for the first time. Biologically, the inhibitory effects of compounds 6 and 21 on NO production in LPS-induced BV-2 microglial cells were better than that of the positive control, with IC 50 values of 6.7 and 5.2 μM, respectively. The antioxidant activity assay showed that compounds 5 , 15 , 17 , and 24 displayed moderate DPPH radical scavenging activity, with IC 50 values ranging from 34.9 to 43.9 μM.

Phthalate esters (PEs) are the most widely used class of plasticizers. Several PEs, however, were found to have adverse effects on the health of animals. A new phthalate-free plasticizer, Eco-DEHCH (bis(2-ethylhexyl) cyclohexane-1,4-dicarboxylate), was recently developed as an ecofriendly replacement for phthalate plasticizers and to be less harmful to organisms. The present study evaluated the long-term toxicity of Eco-DEHCH in Wistar Han rats to explore adverse effects and predict hazardous potential to humans. Forty male and forty female Wistar Han rats were exposed to Eco-DEHCH in dietary feed for 52 weeks, and their hematologic, coagulation, and serum biochemical parameters were monitored. The rats were subjected to close clinical, ophthalmic, and histopathologic examinations and urinalysis throughout the consumption of Eco-DEHCH. The effects of this plasticizer on food consumption and organ weight were also determined. Chronic exposure to Eco-DEHCH was generally safe, although it also resulted in α 2u -globulin accumulation, a parameter with no human relevance. In conclusion, Eco-DEHCH can serve as a safe and promising alternative plasticizer., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Background: The ester-synthesis enzymes influenced by environmental factors during Daqu-making process largely determine the flavor of Chinese liquor, but the main ester-synthesis enzyme and its key influencer remain unclear. Here, the volatile ester profiles over the whole Daqu-making process, under different treatments, for at least 90 days, were carefully analyzed, and the potential ester-synthesis enzymes, as well as their dependently environmental factors, were explored., Results: In the detected 46 volatile esters, only the short-chain (C4-C8) and medium-chain (C9-C13) ester content obviously changed, as the primary contributor discriminating different samples. Their trends were both consistent with that of the alcohols and the primary metabolism, which included alcohol acyltransferases (AATs) reaction with alcohols and acyl-CoAs as the substrates. Among the potential ester-synthesis enzymes, the typical AAT activity also exhibited the highest correlation with the short- and medium-chain esters (r > 0.78, P < 0.05). The Mantel test between environmental factors and ester production showed that temperature of Daqu was directly correlated with the short-chain esters (r = 0.58, P < 0.01) and AAT activity (r = 0.56, P < 0.01). Further, the short- and medium-chain ester content in Daqu under the treatment nearer to the reported optimal temperature of 40-50 °C of AATs reaction was overall higher than that of the other treatment Daqu., Conclusion: This study revealed that the temperature-dependent AATs reaction was the main enzymatic method producing the short- and medium-chain esters over the whole Daqu-making process. The results could contribute to the flavor improvement of Baijiu. © 2022 Society of Chemical Industry., (© 2022 Society of Chemical Industry.)

The palladium-catalyzed Sonogashira coupling of α, β-unsaturated acid derivatives offers a diversity-oriented synthetic strategy for cross-conjugated enynones. However, the susceptibility of the unsaturated C-C bonds adjacent to the carbonyl group toward Pd catalysts makes the direct conversion of α, β-unsaturated derivatives as acyl electrophiles to cross-conjugated ketones rare. This work presents a highly selective C-O activation approach to prepare cross-conjugated enynones using α, β-unsaturated triazine esters as acyl electrophiles. Under base and phosphine ligand-free conditions, NHC-Pd(II)-Allyl precatalyst alone catalyzed the cross-coupling of α, β-unsaturated triazine esters with terminal alkynes efficiently, yielding 31 cross-conjugated enynones with diverse functional groups. This method demonstrates the potential of triazine-mediated C-O activation for preparing highly functionalized ketones.

1,2,4-Triazole and 1,2,4-triazoline are important components of bioactive molecules and catalysts employed in organic synthesis. Therefore, the efficient synthesis of these components has received significant research attention. However, studies on their structural diversity remain lacking. Previously, we developed chiral phase-transfer-catalyzed asymmetric reactions of α -imino carbonyl compounds with α , β -unsaturated carbonyl compounds and haloalkanes. In this study, we demonstrate the formal [3 + 2] cycloaddition reaction of α -imino esters with azo compounds under Brønsted base catalysis, resulting in the corresponding 1,2,4-triazolines in high yields. The results revealed that a wide range of substrates and reactants can be applied, irrespective of their steric and electronic characteristics. The present reaction made the general preparation of 3-aryl pentasubstituted 1,2,4-triazolines possible for the first time. Furthermore, a mechanistic study suggested that the reaction proceeds without isomerization into the aldimine form.

Structural modification of natural products is one of the important ways in the discovery of novel pesticides. Based on a diversity-oriented synthesis strategy, herein, two series of amide/ester derivatives (52 compounds) were obtained by opening the lactone of osthole. Interestingly, the effect of different concentrations of aq. sodium hydroxide on the ratio of two isomers ( cis - and trans -2 ) was investigated, and a magical phenomenon of ultraviolet (UV) light irradiation on intertransformation of two isomers ( cis - and trans -2 ) was observed. Against Mythimna separata , when compared with the precursor osthole, compounds 4b , 4l , 5l , 5m , 7h , 7l , and 7m displayed more pronounced growth inhibitory activity with the final mortality rates of 62.0-68.9%. Compounds 4b , 4i , and 5m showed 5.7-6.6 times stronger acaricidal activity against Tetranychus cinnabarinus than osthole, and notably, control effects of compounds 4i and 5m were 2.4- and 2.7-fold that of osthole in the management of T. cinnabarinus in the greenhouse. Scanning electron microscopy (SEM) images of the epidermis of 5m- treated T. cinnabarinus indicated that compound 5m can destroy the mite cuticle layer. Compounds 4b and 5m can be used as leads to further explore more promising pesticidal agents.

Wax ester synthases (WSs) utilize a fatty alcohol and a fatty acyl-coenzyme A (activated fatty acid) to synthesize the corresponding wax ester. There is much interest in developing novel cell factories that can produce shorter esters, e.g., fatty acid ethyl esters (FAEEs), with properties similar to biodiesel in order to use these as transportation fuels. However, ethanol is a poor substrate for WSs, and this may limit the biosynthesis of FAEEs. Here, we implemented a random mutagenesis approach to enhance the catalytic efficiency of a WS from Marinobacter hydrocarbonoclasticus (MhWS2, encoded by the ws2 gene). Our selection system was based on FAEE formation serving as a detoxification mechanism for excessive oleate, where high WS activity was essential for a storage-lipid free yeast to survive. A random mutagenesis library of ws2 was used to transform the storage-lipid free yeast, and mutants could be selected by plating the transformants on oleate containing plates. The variants encoding WS with improved activity were sequenced, and an identified point mutation translated into the residue substitution at position A344 was discovered to substantially increase the selectivity of MhWS2 toward ethanol and other shorter alcohols. Structural modeling indicated that an A344T substitution might affect the alcohol selectivity due to change of both steric effects and polarity changes near the active site. This work not only provides a new WS variant with altered selectivity to shorter alcohols but also presents a new high-throughput selection system to isolate WSs with a desired selectivity. KEY POINTS: • The work provides WS variants with altered substrate preference for shorter alcohols • A novel method was developed for directed evolution of WS of desired selectivity., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Purpose: Although curcumin (Cur) has powerful pharmacological effects, its use in medicine has not been established yet. The oral bioavailability (BA) of Cur is limited because of its poor water solubility. The purpose of this study was to confirm whether cationic N,N-dimethyl amino acid esters of Cur could act as prodrugs and improve its water solubility and oral bioavailability., Methods: Two N,N-dimethyl amino acid esters of Cur were synthesized. The hydrolysis profile of the esters was evaluated using rat and human microsomes. A pharmacokinetic study after oral administration of the Cur ester derivatives was performed in rats and compared to the administration of suspended or dissolved Cur formulation. The anti-inflammatory effects of the Cur derivatives were evaluated using macrophage RAW 264.7 stimulated with lipopolysaccharide., Results: Cur ester derivatives showed  > 200 mM water solubility. The derivatives were reconverted to the parent compound (Cur) after cleavage of the ester bonds by microsomal esterase, indicating that the compounds could act as Cur prodrugs. The Cur prodrugs enhanced the absolute oral bioavailability of Cur by a 9- and threefold increase of suspended and dissolved Cur administration, respectively, thereby improving intestinal absorption. Cur prodrugs strongly attenuated COX2, iNOS, and ERK phosphorylation., Conclusions: The cationic N,N-dimethyl amino acid ester prodrugs of Cur improved the water solubility of Cur and enhanced oral bioavailability in rats. These Cur prodrugs may be good candidates for developing medicinal options previously unavailable due to the poor water solubility and oral BA of Cur., (© 2023. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

As a traditionally used packaging material, natural cellulose-based paper has poor barrier properties to water and oxygen, which severely limits its wide application in food packaging. In this study, we report a new sustainable approach to producing hydrophobic, high-barrier, and antibacterial packaging materials from cellulose paper. In this process, commercially available microcrystalline cellulose was first modified by long-chain stearic acid to form hydrophobic microcrystalline cellulose ester and then mixed with stearic acid as filler in the subsequent surface coating of bagasse fibre paper. The microcrystalline cellulose ester/stearic acid-coated paper (MSP) exhibited good water repellency and oxygen barrier activity due to a continuous hydrophobic film that formed, which completely covered the pores of the original bagasse fibre paper. The coated MSP sample also showed excellent dimensional stability in water and a good wet tensile strength of 16 MPa. In addition, poly(hexamethylene guanidine) (PHMG) was chemically grafted onto the free carboxyl groups of the MSP surface layer, and the resulting MSP-g-PHMG samples exhibited excellent antibacterial activity against Escherichia coli and Listeria monocytogenes. The biodegradable cellulose-based MSP-g-PHMG sample significantly delayed the decay of raspberry during storage, indicating its potential application in food packaging., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier B.V.)

Phthalic acid esters (PAEs) are a group of organic compounds that show vulnerability effects in different stages of human development. In this work, two sensitive and efficient impedimetric biosensors (IBs) were introduced and their interactions with four PAEs, namely dibutyl phthalate (DBP), dimethyl phthalate (DMP), di(2-ethylhexyl) phthalate (DEHP), and dicyclohexyl phthalate (DCHP), in aqueous solutions with these biosensors were separately investigated via electrochemical impedance spectroscopy (EIS). The surface of a copper electrode was modified by azolla fern dried powder (AZ) and magnetite-modified azolla nanocomposites (MAZ NCs) to form an azolla-based impedimetric biosensor (AZIB) and magnetite azolla nanocomposite-based impedimetric nanobiosensor (MAZIB), respectively. Determinations of PAEs with the designed biosensors were conducted based on their blocking effect on the biosensor surface to ferrous ions oxidation. After each impedimetric measurement, the electrode surface was covered again with the modifier. Nyquist plots were obtained and indicated that the charge-transfer resistance ( R CT ) values of the bare electrode, AZIB, and MAZIB without injection of PAEs were 468.8, 438.7, and 285.1 kΩ, respectively. After the separate injection of DBP, DMP, DEHP, and DCHP (3 μg L -1 ) on the surface of AZIB and MAZIB, R CT values were obtained as 563.9, 588.5, 548.7, and 570.1 kΩ for AZIB and 878.2, 1219.2, 754.3, and 814.7 kΩ for MAZIB, respectively. It was observed that the PAE blockers with a smaller structure provided better point-by-point coverage of the surface, which led to a bigger shift in R CT . The linear relationship between the EIS responses and each PAE concentration was investigated in the range of 0.1-1000 μg L -1 . The limit of detection (LOD) and limit of quantification (LOQ) values were obtained in the ranges of 0.003-0.005 μg L -1 and 0.010-0.016 μg L -1 for AZIB and 0.008-0.009 μg L -1 and 0.027-0.031 μg L -1 for MAZIB, respectively. The results showed that these biosensors can be used to determine PAEs in real aqueous samples with good relative recoveries ranging from 93.0-97.7% (RSD < 2.58%) for AZIB and 93.3-99.3% (RSD < 2.45%) for MAZIB. The results confirmed that these impedimetric biosensors offer high sensitivity and performance for the determination of trace PAEs in aqueous samples.

Organophosphate esters (OPEs) are emerging contaminants of growing concern, and there is limited information about the bacterial transformation of OPEs. In this study, we investigated the biotransformation of tris(2-butoxyethyl) phosphate (TBOEP), a frequently detected alkyl-OPE by a bacterial enrichment culture under aerobic conditions. The enrichment culture degraded 5 mg/L TBOEP following the first-order kinetics with a reaction rate constant of 0.314 h -1 . TBOEP was mainly degraded via ether bond cleavage, evidenced by the production of bis(2-butoxyethyl) hydroxyethyl phosphate, 2-butoxyethyl bis(2-hydroxyethyl) phosphate, and 2-butoxyethyl (2-hydroxyethyl) hydrogen phosphate. Other transformation pathways include terminal oxidation of the butoxyethyl group and phosphoester bond hydrolysis. Metagenomic sequencing generated 14 metagenome-assembled genomes (MAGs), showing that the enrichment culture primarily consisted of Gammaproteobacteria, Bacteroidota, Myxococcota, and Actinobacteriota. One MAG assigned to Rhodocuccus ruber strain C1 was the most active in the community, showing upregulation of various monooxygenase, dehydrogenase, and phosphoesterase genes throughout the degradation process, and thus was identified as the key degrader of TBOEP and the metabolites. Another MAG affiliated with Ottowia mainly contributed to TBOEP hydroxylation. Our results provided a comprehensive understanding of the bacterial TBOEP degradation at community level., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Ltd.)

Several new acridinium esters 2-9 having their central acridinium ring bearing a 9-(2,5-dimethylphenoxycarbonyl), 9-(2,6-bis(trifluoromethyl)phenoxycarbonyl) or 9-(2,6-dinitrophenoxycarbonyl) group, and a 10-methyl, 10-(3-(succinimidyloxycarbonyl)propyl), 10-(5-(succinimidyloxycarbonyl)pentyl), or 10-(10-(succinimidyloxycarbonyl)decyl) group, have been synthesized and their chemiluminescent properties have been tested. The 2,5-dimethylphenyl acridinium esters emit light slowly (glow) when treated with alkaline hydrogen peroxide, while the 2,6-dinitrophenyl and 2,6-bis(trifluoromethyl)phenyl esters emit light rapidly (flash). The substituent at the 10 position affects the hydrolytic stabilities of the compounds., (© 2023 John Wiley & Sons Ltd.)

Oleanolic (OA) and glycyrrhetinic acids (GE), as well as their derivatives, show a variety of pharmacological properties. Their crystal structures provide valuable information related to the assembly modes of these biologically active compounds. In the known-to-date crystals of OA esters, their 11-oxo derivatives, and GE ester crystals, triterpenes associate, forming different types of ribbons and layers whose construction is based mainly on van der Waals forces and weak C-H···O interactions. New crystal structures of 11-oxo OA methyl ester and the polymorph of OA butyl ester reveal an alternative aggregation mode. Supramolecular architectures consist of helical chains which are stabilized by hydrogen bonds of O-H···O type. It was found that two polymorphic forms of butyl OA ester (layered and helical) are related monotropically. In a structure of metastable form, O-H···O hydrogen bonds occur, while the thermodynamically preferred phase is governed mainly by van der Waals interactions. The intermolecular interaction energies calculated using CrystalExplorer, PIXEL, and Psi4 programs showed that even in motifs formed through O-H···O hydrogen bonds, the dispersive forces have a significant impact.

Novel acridinium esters containing several methyl groups, at least one of which is in the 1 or 8-position, have been synthesized and their structures established. The influence of the methyl substituents on the chemiluminescent properties of the synthesized acridinium esters has been investigated.

Biodiesel is a biological renewable source produced from the conversion of triglycerides to alkyl esters. Palm oil is one of the most used lipid feedstocks for biodiesel production. It becomes necessary to optimize the transesterification reaction parameters to reduce the cost and enhance the quality of biodiesel. This study focuses on the use of homogenous sulfuric acid as a catalyst for the transesterification of palm fatty acids to methyl esters in a batch-scale reactor. A novel examination of transesterification reaction input parameters using the technique for order performance by similarity to ideal solution optimization technique and the effect of these parameters on yield, viscosity, and density of palm biodiesel using 3D surface graphs is investigated in this research. The present optimization approach is implemented to find out the optimum ranking of biodiesel production. From the experimental and numerical simulation, optimum results were observed at the catalyst concentration of 6% (w/w), reaction temperature of 70 °C, the reaction time of 120 min, and alcohol to oil molar ratio of 30:1 at which yield of 95.35%, viscosity of 5.0 cSt, and density of 880 kg/m 3 of palm biodiesel were obtained. The different physicochemical properties of produced palm methyl esters are obtained within standards set by international authorities. Selected optimized process parameters can be used for commercial-scale biodiesel production., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Pesticides play an important role in crop disease and pest control. However, their irrational use leads to the emergence of drug resistance. Therefore, it is necessary to search for new pesticide-lead compounds with new structures. We designed and synthesized 33 novel pyrimidine derivatives containing sulfonate groups and evaluated their antibacterial and insecticidal activities. Results: Most of the synthesized compounds showed good antibacterial activity against Xanthomonas oryzae pv. Oryzae ( Xoo ), Xanthomonas axonopodis pv. Citri ( Xac ), Pseudomonas syringae pv. actinidiae ( Psa ) and Ralstonia solanacearum (Rs), and certain insecticidal activity. A 5 , A 31 and A 33 showed strong antibacterial activity against Xoo , with EC 50 values of 4.24, 6.77 and 9.35 μg/mL, respectively. Compounds A 1 , A 3 , A 5 and A 33 showed remarkable activity against Xac (EC 50 was 79.02, 82.28, 70.80 and 44.11 μg/mL, respectively). In addition, A 5 could significantly improve the defense enzyme (superoxide dismutase, peroxidase, phenylalanine ammonia-lyase and catalase) activity of plants against pathogens and thus improve the disease resistance of plants. Moreover, a few compounds also showed good insecticidal activity against Plutella xylostella and Myzus persicae . The results of this study provide insight into the development of new broad-spectrum pesticides.

Introducing vinyl groups onto the backbone of technical lignin provides an opportunity to create highly reactive renewable polymers suitable for radical polymerization. In this work, the chemical modification of softwood kraft lignin was pursued with etherification, followed by direct esterification with acrylic acid (AA). In the first step, phenolic hydroxyl and carboxylic acid groups were derivatized into aliphatic hydroxyl groups using ethylene carbonate and an alkaline catalyst. The lignin was subsequently fractionated using a downward precipitation method to recover lignin of defined molar mass and solubility. After recovery, the resulting material was then esterified with AA, resulting in lignin with vinyl functional groups. The first step resulted in approximately 90% of phenolic hydroxyl groups being converted into aliphatic hydroxyls, while the downward fractionation resulted in three samples of lignin with defined molar masses. For the esterification reaction, the weight ratio of reagents, reaction temperature, and reaction time were evaluated as factors that would influence the modification efficacy. 13 C NMR spectroscopy analysis of lignin samples before and after esterification showed that the optimized reaction conditions could reach approximately 40% substitution of aliphatic hydroxyl groups. Both steps only used lignin and the modifying reagent (no solvent), with the possibility of recovery and reuse of the reagent by dilution and distillation. An additional second esterification step of the resulting lignin sample with acetic acid or propionic acid converted 90% of remaining hydroxyl groups into short-chain carbon aliphatic esters, making a hydrophobic material suitable for further copolymerization with synthetic hydrophobic monomers.

Phthalate acid esters (PAEs) are commonly used plastic additives, not chemically bound to the plastic that migrate into surrounding environments, posing a threat to environmental and human health. Dibutyl phthalate (DBP) and di(2-ethylhexyl) phthalate (DEHP) are two common PAEs found in agricultural soils, where degradation is attributed to microbial decomposition. Yet the impact of the plastic matrix on PAE degradation rates is poorly understood. Using 14 C-labelled DBP and DEHP we show that migration from the plastic matrix into soil represents a key rate limiting step in their bioavailability and subsequent degradation. Incorporating PAEs into plastic film decreased their degradation in soil, DBP (DEHP) from 79% to 21% (9% to <1%), over four months when compared to direct application of PAEs. Mimicking surface soil conditions, we demonstrated that exposure to ultraviolet radiation accelerated PAE mineralisation twofold. Turnover of PAE was promoted by the addition of biosolids, while the presence of plants and other organic residues failed to promote degradation. We conclude that PAEs persist in soil for longer than previously thought due to physical trapping within the plastic matrix, suggesting PAEs released from plastics over very long time periods lead to increasing levels of contamination., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Excess waste-activated sludge (WAS) is a major biosolid management problem due to its biohazardous and recalcitrant content of phthalate esters (PAEs). This study aimed to assess the combined use of biopolymer, poly-3-hydroxybutyrate and peroxymonosulfate to degrade PAEs and decontaminate WAS. Poly-3-hydroxybutyrate was biosynthesized by Cupriavidus sp. L7L. The combined poly-3-hydroxybutyrate and peroxymonosulfate process removed 86 % of PAEs from WAS in 12 h. The carbonyl groups of poly-3-hydroxybutyrate were conducive to peroxymonosulfate activation leading to PAE degradation followed the radical pathway and surface-mediated electron transfer. Poly-3-hydroxybutyrate and peroxymonosulfate also enriched the PAE-biodegrading microbes in WAS. The microbial population and the functional composition in response to peroxymonosultate treatment was identified, with the genus Sulfurisoma being the most abundant. This synergistic treatment, i.e., advanced oxidation process, was augmented by highly promising microbial polyesters, exhibited important implications for WAS pretreatment toward circular bioeconomy that encompasses carbon-neutral biorefinery and mitigate pollution., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Amicoumacins are a family of antibiotics with a variety of important bioactivities. A concise and efficient method was developed for synthesizing the amino acid component of amicoumacins via the corresponding dihydrooxazine intermediate. The dihydrooxazine ring was formed with complete stereoselectivity through an intramolecular conjugate addition of a δ-trichloroacetimidoyloxy-α,β-unsaturated ester, which was obtained from a known 4,6-O-p-methoxybenzylidene-protected d-glucose. The synthesis developed in this study can be used to synthesize the building blocks of amicoumacins and can likely be adapted for the synthesis of other types of molecules possessing dihydrooxazine rings or amino alcohol moieties., (© The Author(s) 2022. Published by Oxford University Press on behalf of Japan Society for Bioscience, Biotechnology, and Agrochemistry.)

Engineering studies of Candida (Pseudozyma) antarctica lipase A (CalA) have demonstrated the potential of this enzyme in the selective hydrolysis of fatty acid esters of different chain lengths. CalA has been shown to bind substrates preferentially through an acyl-chain binding tunnel accessed via the hydrolytic active site; it has also been shown that selectivity for substrates of longer or shorter chain length can be tuned, for instance by modulating steric hindrance within the tunnel. Here we demonstrate that, whereas the tunnel region is certainly of paramount importance for substrate recognition, residues in distal regions of the enzyme can also modulate substrate selectivity. To this end, we investigate variants that carry one or more substitutions within the substrate tunnel as well as in distal regions. Combining experimental determination of the substrate selectivity using natural and synthetic substrates with computational characterization of protein dynamics and of tunnels, we deconvolute the effect of key substitutions and demonstrate that epistatic interactions contribute to procuring selectivity toward either long-chain or short/medium-chain fatty acid esters. We demonstrate that various mechanisms contribute to the diverse selectivity profiles, ranging from reshaping tunnel morphology and tunnel stabilization to obstructing the main substrate-binding tunnel, highlighting the dynamic nature of the substrate-binding region. This work provides important insights into the versatility of this robust lipase toward diverse applications.

In cancer cells, glutaminolysis is the primary source of biosynthetic precursors. Recent efforts to develop amino acid analogues to inhibit glutamine metabolism in cancer have been extensive. Our lab recently discovered many L-γ-methyleneglutamic acid amides that were shown to be as efficacious as tamoxifen or olaparib in inhibiting the cell growth of MCF-7, SK-BR-3, and MDA-MB-231 breast cancer cells after 24 or 72 h of treatment. None of these compounds inhibited the cell growth of nonmalignant MCF-10A breast cells. These L-γ-methyleneglutamic acid amides hold promise as novel therapeutics for the treatment of multiple subtypes of breast cancer. Herein, we report our synthesis and evaluation of two series of tert-butyl ester and ethyl ester prodrugs of these L-γ-methyleneglutamic acid amides and the cyclic metabolite and its tert-butyl esters and ethyl esters on the three breast cancer cell lines MCF-7, SK-BR-3, and MDA-MB-231 and the nonmalignant MCF-10A breast cell line. These esters were found to suppress the growth of the breast cancer cells, but they were less potent compared to the L-γ-methyleneglutamic acid amides. Pharmacokinetic (PK) studies were carried out on the lead L-γ-methyleneglutamic acid amide to establish tissue-specific distribution and other PK parameters. Notably, this lead compound showed moderate exposure to the brain with a half-life of 0.74 h and good tissue distribution, such as in the kidney and liver. Therefore, the L-γ-methyleneglutamic acid amides were then tested on glioblastoma cell lines BNC3 and BNC6 and head and neck cancer cell lines HN30 and HN31. They were found to effectively suppress the growth of these cancer cell lines after 24 or 72 h of treatment in a concentration-dependent manner. These results suggest broad applications of the L-γ-methyleneglutamic acid amides in anticancer therapy., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Herein, we describe an iron-catalyzed benzylic C-H borylation reaction. The reaction targets primary and secondary C(sp 3 )-H bonds to deliver high-value boronic esters under mild conditions with short (7-8 min) reaction times. Functional groups are well tolerated, and complete site selectivity is observed in the presence of multiple benzylic C-H bonds.

An efficient synthetic method was developed to access isoquinoline-derived diene esters from enynones and isoquinoline- N -oxides in an atom-economic manner. The isoquinoline-substituted diene esters were obtained in moderate to excellent yields via [3 + 2]-cycloaddition and isoxazole ring opening followed by a [1,5]-sigmatropic rearrangement reaction, which resulted in one C-C and two C-O bond formations. Further, quinolin-2(1 H )-ylidene-substituted 1,5-diones were achieved by reaction of enynones with quinoline- N -oxides in very good to high yields.

A new method to access β-keto-gem-diborylalkanes, by direct deoxygenative radical addition of aromatic carboxylic acids to gem-dibortlalkenes, is described. The reaction proceeds under mild photoredox catalysis and involves the photochemical C-O bond activation of aromatic carboxylic acids in the presence of PPh 3 . It generates an acyl radical, which further undergoes an additional reaction with gem-diborylalkenes to form an α-gem-diboryl alkyl radical intermediate, which then reduces to the corresponding anion, which after protonation, affords the β-keto-gem-diborylalkane product. Moreover, the same scenario has been extended to the vinyl boronic esters, for example, gem-(Ar, Bpin)-alkenes, and gem-(Alkyl, Bpin)-alkenes. Importantly, this protocol provides a general platform for the late-stage functionalization of bio-active and drug molecules containing a carboxylic acid group., (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)

Numerous chemical modifications of hyaluronic acid (HA) have been explored for the formation of degradable hydrogels that are suitable for a variety of biomedical applications, including biofabrication and drug delivery. Thiol-ene step-growth chemistry is of particular interest due to its lower oxygen sensitivity and ability to precisely tune mechanical properties. Here, we utilize an aqueous esterification route via reaction with carbic anhydride to synthesize norbornene-modified HA (NorHA CA ) that is amenable to thiol-ene crosslinking to form hydrolytically unstable networks. NorHA CA is first synthesized with varying degrees of modification (∼15-100%) by adjusting the ratio of reactive carbic anhydride to HA. Thereafter, NorHA CA is reacted with dithiol crosslinker in the presence of visible light and photoinitiator to form hydrogels within tens of seconds. Unlike conventional NorHA, NorHA CA hydrogels are highly susceptible to hydrolytic degradation through enhanced ester hydrolysis. Both the mechanical properties and the degradation timescales of NorHA CA hydrogels are tuned via macromer concentration and/or the degree of modification. Moreover, the degradation behavior of NorHA CA hydrogels is validated through a statistical-co-kinetic model of ester hydrolysis. The rapid degradation of NorHA CA hydrogels can be adjusted by incorporating small amounts of slowly degrading NorHA macromer into the network. Further, NorHA CA hydrogels are implemented as digital light processing (DLP) resins to fabricate hydrolytically degradable scaffolds with complex, macroporous structures that can incorporate cell-adhesive sites for cell attachment and proliferation after fabrication. Additionally, DLP bioprinting of NorHA CA hydrogels to form cell-laden constructs with high viability is demonstrated, making them useful for applications in tissue engineering and regenerative medicine.

Palladium-catalyzed Suzuki reactions of brominated flavin derivatives (5-deazaflavins, alloxazines, and isoalloxazines) with boronic acids or boronic acid esters that occur readily under mild conditions were shown to be an effective tool for the synthesis of a broad range of 7/8-arylflavins. In general, the introduction of an aryl/heteroaryl group by means of a direct C-C bond has been shown to be a promising approach to tuning the photophysical properties of flavin derivatives. The aryl substituents caused a bathochromic shift in the absorption spectra of up to 52 nm and prolonged the fluorescence lifetime by up to 1 order of magnitude. Moreover, arylation of flavin derivatives decreased their ability to generate singlet oxygen.

Directing groups play an important role in controlling the selectivity of C-H bond activation. Here we demonstrate that for iron, the nature of the directing group ( e.g. , ketone, ester, or amide) influences the C-H activation process. In this study the C-H bond activation step either occurs with or without the assistance of the directing group resulting in distinct cis - and trans -isomers of the corresponding iron hydride.

The direct mechanocatalytic Suzuki-Miyaura coupling reaction, utilizing palladium milling balls as active catalysts, was investigated regarding the physical state of the reagents and the reaction phase. The substitution patterns and functional groups of different aryl iodides were varied and different boronic acid derivates were utilized to achieve a wide range of substrate combinations. In the neat grinding experiments, liquid aryl iodides were more reactive than solid ones and a steric influence of the substituents, especially pronounced in ortho compounds, was observed. In order to overcome the general low reactivity of the solid phase, several liquid-assisted grinding experiments were conducted and the influence of substrate solubility and catalyst wettability analyzed. Among all LAG additives, EtOH showed the greatest impact on the reactivity, as it converts boronic acid derivatives into liquid and reactive esters under mechanochemical conditions, significantly speeding up the reaction.

As a representative class of sustainable polymer materials, biodegradable polymers have attracted increasing interest in recent years. Despite significant advance of related polymerization techniques, realizing high sequence-control and easy-handling in ring-opening (co)polymerizations still remains a central challenge. To this end, a promising solution is the development of valence-variable metal-based catalysts for redox-induced switchable polymerization of cyclic esters, cyclic ethers, epoxides, and CO 2 . Through a valence-determined electron effect, the switch between different catalytically active states as well as dormant state contributes to convenient formation of polymer products with desired microstructures and various practical performances. This redox-controlled switchable strategy for controlled synthesis of polymers is overviewed in this Review with a focus on potential applications and challenges for further studies., (© 2022 Wiley-VCH GmbH.)

Chemical synthesis of proteins bearing base-labile post-translational modifications (PTMs) is a challenging task. For instance, O-acetylation and S-palmitoylation PTMs cannot survive Fmoc removal conditions during Fmoc-solid phase peptide synthesis (SPPS). In this work, we developed a new Boc-SPPS-based strategy for the synthesis of peptide C-terminal salicylaldehyde (SAL) esters, which are the key reaction partner in Ser/Thr ligation and Cys/Pen ligation. The strategy utilized the semicarbazone-modified aminomethyl (AM) resin, which could support the Boc-SPPS and release the peptide SAL ester upon treatment with TFA/H 2 O and pyruvic acid. The non-oxidative aldehyde regeneration was fully compatible with all the canonical amino acids. Armed with this strategy, we finished the syntheses of the O-acetylated protein histone H3(S10ac, T22ac) and the hydrophobic S-palmitoylated peptide derived from caveolin-1., (© 2022 Wiley-VCH GmbH.)

Curdlan, a linear β-1,3-glucan, was reacted with glutaric anhydride and heptanoyl chloride to afford thermoplastic curdlan esters (CrdE(HepGlu)) with a carboxylic acid side chain. CrdE(HepGlu) with a degree of substitution of the glutaric acid monoester moiety (DS Glu ) in the range of 0-0.58 and that of the heptanoate moiety (DS Hep  = 3 - DS Glu ) was prepared. The esterification of the hydroxy groups in the glucan skeleton effectively caused the cleavage of the interchain hydrogen bonds of curdlan and enhanced the formability of CrdE(HepGlu). Moreover, the flexible carboxylic acid side chain moderately affected hydrogen bonding. Thus, the glass transition temperature of CrdE(HepGlu), estimated by differential scanning calorimetry, increased with increasing DS Glu . CrdE(HepGlu) with DS Glu between 0 and 0.58 displayed high solubility in organic solvents and thermoplasticity, enabling the formation of homogeneous and free-standing films by solution casting. The mechanical properties of CrdE(HepGlu) films were evaluated by a stress-strain test, which showed that Young's modulus and the maximum stress increased with increasing DS Glu . CrdE(HepGlu) exhibited higher mechanical strength than non-hydrogen-bonded curdlan triheptanoate and hydrogen-bonded curdlan alkylcarbamates, with thermal stability comparable to that of thermally stable curdlan esters. In addition, these properties can be regulated by controlling DS Glu ., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)