Alkyl Aryl Ethers Research Articles

Exploring the Darobactin Class of Antibiotics: A Comprehensive Review from Discovery to Recent Advancements.

The prevalence of antimicrobial resistance in Gram-negative bacteria poses a greater challenge due to their intrinsic resistance to many antibiotics. Recently, darobactins have emerged as a novel class of antibiotics originating from previously unexplored Gram-negative bacterial species such as Photorhabdus, Vibrio, Pseudoalteromonas and Yersinia. Darobactins belong to the ribosomally synthesized and post-translationally modified peptide (RiPP) class of antibiotics, exhibiting selective activity against Gram-negative bacteria. They target the β-barrel assembly machinery (BAM), which is crucial for the maturation and insertion of outer membrane proteins in Gram-negative bacteria. The dar operon in the producer's genome encodes for the synthesis of darobactins, which are characterized by a fused ring system connected via an alkyl-aryl ether linkage (C-O-C) and a C-C cross-link. The enzyme DarE, using the radical S-adenosyl-l-methionine (rSAM), facilitates the formation of these bonds. Biosynthetic manipulation of the darobactin gene cluster, along with its expression in a surrogate host, has enabled access to diverse darobactin analogues with variable antibiotic activities. Recently, two independent research groups successfully achieved the total synthesis of darobactin, employing Larock heteroannulation to construct the bicyclic structure. This paper presents a comprehensive review of darobactins, encompassing their discovery through to the most recent advancements.

Highly uncondensed lignin extraction in the novel green L-cysteine/lactic acid cosolvent system

Enhancing the efficient isolation of proto-lignin from lignocellulose using sustainable, environmentally friendly solvents has consistently been a key focus in the lignin-first biorefinery strategy for the past years. At the same time, achieving efficient extraction of highly uncondensed active lignin under acidic conditions has posed an insurmountable challenge. In this study, we develop an L-cysteine-assisted binary acidic cosolvent that efficiently separates the uncondensed lignin under 80 ∼ 90 °C treatment, resulting in a lighter color and a recovery yield of up to 60 %. The corresponding delignification rate reached 82.6 %. The obtained lignin exhibited an ideal retention rate (maximum 84.5 %) of alkyl aryl ether bonds (β–O–4) relative to the native lignin in raw material. The resulting residue was free from cellulose decomposition and yielded over 90 % cellulose with a surface-esterified structure. This study establishes a one-step L-cysteine-assisted stabilization methodology that overcomes the challenges of lignin condensation and allows for the fractionation of lignocellulose into highly uncondensed lignin and high-quality cellulose, thus offering new solutions for biorefinery.

Phytofabrication of biocompatible zinc oxide nanoparticle using Gymnema sylvestre and its potent in vitro antibacterial, antibiofilm, and cytotoxicity against human breast cancer cells (MDA-MB-231).

The increasing incidence of breast cancer and bacterial biofilm in medical devices significantly heightens global mortality and morbidity, challenging synthetic drugs. Consequently, greener-synthesized nanomaterials have emerged as a versatile alternative for various biomedical applications, offering new therapeutic avenues. This study explores the synthesis of biocompatible zinc oxide (ZnONPs) nanoparticles using Gymnema sylvestre and its antibacterial, antibiofilm, and cytotoxic properties. Characterization of ZnONPs inferred that UV-Vis spectra exhibited a sharp peak at 370nm. Fourier transform infrared spectroscopical analysis revealed the presence of active functional groups such as aldehyde, alkyne, cyclic alkene, sulfate, alkyl aryl ether, and Zn-O bonds. X-ray diffraction analysis results confirmed the crystalline nature of the nanoparticle. Scanning electron microscope analysis evidenced hexagonal morphology, and energy-dispersive X-ray analysis confirmed zinc content. High-resolution transmission electron microscope analysis showed hexagonal and rod-shaped ZnONPs with a size of 5nm. Zeta potential results affirmed the stability of nanoparticles. The ZnONPs effectively inhibited gram-positive (18-20mm) than gram-negative (12-18mm) bacterial pathogens with lower bacteriostatic and higher bactericidal values. Biofilm inhibitory property inferred ZnONPs were more effective against gram-positive (38-94%) than gram-negative bacteria (27-86%). The concentration of ZnONPs to exert 50% biofilm-inhibitory is lower against gram-positive bacteria (179.26-203.95μg/mL) than gram-negative bacteria (201.46-236.19μg/mL). Microscopic visualization inferred that at 250μg/mL, ZnONPs strongly disrupted biofilm formation, as evidenced by decreased biofilm density and altered architecture. The cytotoxicity of ZnONPs against breast cancer cells showed a dose-dependent reduction in cell viability with an IC50 value of 19.4µg/mL. AO/EB staining indicated early and late apoptotic cell death of breast cancer cells under fluorescence microscopy. The results of hemolytic activity validated the biocompatibility of the ZnONPs. Thus, the unique properties of the green-synthesized ZnONPs suggest their potential as effective drug carriers for targeted delivery in cancer therapy and the treatment of biofilm-related infections.

Optimization and Characterization of Biochar Obtained from the Weedy Biomass of Calotropis gigantea Using Vacuum Pyrolysis

The excessive growth of invasive weeds causes adverse economic and environmental effects. In the present study, invasive weed Calotropis gigantea was pyrolyzed under optimized parameters of 450° and 50-100 mm particle size for 1.00 hour of reaction time for biochar production. The biochar was characterized by the presence of a high carbon content of 64.65% and low H/C and O/C molar ratios of 0.08 and 0.15, respectively. The biochar was observed with high surface area of 99.91m2/g and pore volume of 0.0398cm3/g along with mineral fractions such as K-1.33%, Na-1.17%, Mg-1.05%. Strong FTIR bands were observed at 1994.1 cm-1, 1110 cm-1, and 745 cm-1, representing allenes (R 2C=C=CR 2), aryl alkyl ethers (R – O – R), and aromatic (C–H) bending. All these parameters indicate its potential in the applications such as carbon sequestration, climate change mitigation, environment pollutants adsorption (both organic and inorganic), and soil improvement.

Assessment of Lignin Residues from Bioethanol Production of Olive Stones as Green Chemical Thickener of Epoxidized Linseed Oil

This work focused on the characterization of lignin residues from bioethanol production of olive stones (OS) and the use of these residues to chemically thicken epoxidized linseed oil (ELO). OS were processed by an acid/steam explosion pretreatment, followed by pre-saccharification, using different enzyme dosages, and simultaneous saccharification and fermentation. The chemical composition of the OS lignin residues was analysed, revealing a high lignin content (66.6–69.5%), and lower quantities of glucan (17.4–19.3%) and xylan (2.8–2.9%). Whereas, the structural properties of OS lignin residues were characterized by Fourier-transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR), thermogravimetric analysis and size exclusion chromatography (SEC). OS lignin residues displayed the main inter-unit linkages (β–β′ resinol (51.0–59.0%), followed by β-O-4′ alkyl aryl ethers (27.0–35.2%) and β-5′ phenylcoumaran (11.4–13.2%) substructures), high molecular weights (22,000–25900 Da), low S/G ratios (1.2–1.5) and phenolic groups content (48–55 mg GAE/g lignin). Moreover, OS lignin residues were dispersed in ELO to obtain thickened formulations, which were characterized by FTIR and NMR. Oil thickening was achieved by promoting the chemical crosslinking between lignocellulose hydroxyl groups and ELO epoxy groups, enabling the compatibilization of both components. Up to tenfold viscosity increment of the resulting thickened formulations in relation to ELO’s viscosity was observed. Besides, thickened formulations exhibited viscoelastic properties, evincing oil structuration to some extent.Graphical

Editing Tetrasubstituted Carbon: Dual C-O Bond Functionalization of Tertiary Alcohols Enabled by Palladium-Based Dyotropic Rearrangement.

Many elegant asymmetric syntheses of enantioenriched tertiary alcohols have been developed, and both the transition metal-catalyzed and the radical-based peripheral functionalization of tertiary alcohols have attracted intensive research interest in recent years. However, directly editing tetrasubstituted carbons remains challenging. Herein, we report a Pd-catalyzed migratory fluoroarylation reaction that converts tertiary alcohols to α-fluorinated tertiary alkyl ethers in good to excellent yields. An unprecedented 1,2-aryl/PdIV dyotropic rearrangement along the C-O bond, integrated in a PdII-catalyzed domino process, is key to the dual functionalization of both the hydroxyl group and the tetrasubstituted carbon. This reaction, which is compatible with a broad range of functional groups, generates a tertiary alkyl fluoride and an alkyl-aryl ether functional group with inversion of the absolute configuration at the tetrasubstituted stereocenter.

Hydrogen-Induced Formation of Surface Acid Sites on Pt/Al(PO3)3 Enables Remarkably Efficient Hydrogenolysis of C-O Bonds in Alcohols and Ethers.

The hydrogenolysis of oxygenates such as alcohols and ethers is central to the biomass valorization and also a valuable transformation in organic synthesis. However, a mild and efficient catalyst system for the hydrogenolysis of a large variety of alcohols and ethers with various functional groups is still underdeveloped. Here, we report an aluminum metaphosphate-supported Pt nanoparticles (Pt/Al(PO3)3) for the hydrogenolysis of a wide variety of primary, secondary, and tertiary alkyl and benzylic alcohols, and dialkyl, aryl alkyl, and diaryl ethers, including biomass-derived furanic compounds, under mild conditions (0.1-1 atm of H2, as low as 70 °C). Mechanistic studies suggested that H2 induces formation of the surface Brønsted acid sites via its cleavage by supported Pt nanoparticles. Accordingly, the high efficiency and the wide applicability of the catalyst system are attributed to the activation and cleavage of C-O bonds by the hydrogen-induced Brønsted acid sites with the assistance of Lewis acidic Al sites on the catalyst surface. The high efficiency of the catalyst implies its potential application in energy-efficient biomass valorization or fine chemical synthesis.

Hydrogen‐Induced Formation of Surface Acid Sites on Pt/Al(PO3)3 Enables Remarkably Efficient Hydrogenolysis of C−O Bonds in Alcohols and Ethers

AbstractThe hydrogenolysis of oxygenates such as alcohols and ethers is central to the biomass valorization and also a valuable transformation in organic synthesis. However, a mild and efficient catalyst system for the hydrogenolysis of a large variety of alcohols and ethers with various functional groups is still underdeveloped. Here, we report an aluminum metaphosphate‐supported Pt nanoparticles (Pt/Al(PO3)3) for the hydrogenolysis of a wide variety of primary, secondary, and tertiary alkyl and benzylic alcohols, and dialkyl, aryl alkyl, and diaryl ethers, including biomass‐derived furanic compounds, under mild conditions (0.1–1 atm of H2, as low as 70 °C). Mechanistic studies suggested that H2 induces formation of the surface Brønsted acid sites via its cleavage by supported Pt nanoparticles. Accordingly, the high efficiency and the wide applicability of the catalyst system are attributed to the activation and cleavage of C−O bonds by the hydrogen‐induced Brønsted acid sites with the assistance of Lewis acidic Al sites on the catalyst surface. The high efficiency of the catalyst implies its potential application in energy‐efficient biomass valorization or fine chemical synthesis.

Direct, Selective α-Aryloxyalkyl Radical Cyanation and Allylation of Aryl Alkyl Ethers.

We report the site-selective α-aryloxyalkyl C-H cyanation and allylation of aryl alkyl ethers using an acridinium photocatalyst with phosphate base under LED irradiation (456 nm). Oxidation of the aryl alkyl ether to its corresponding radical cation by the excited stated photocatalyst allowed facile deprotonation of the ArOC(sp3)-H bond to afford an α-aryloxyalkyl radical, which was trapped with sulfone substrates, resulting in expulsion of a sulfonyl radical and formation of allylated or cyanated products.

Characterization of Distillation and Redistillation Product of Coconut Shell Liquid Smoke at Various Temperatures

This study investigates the impact of distillation temperature on phenol content in coconut shell liquid smoke, a product derived from pyrolysis and subsequent condensation processes. Liquid smoke, renowned for its versatile applications including preservation, antioxidation, antiseptic, and antibacterial properties, necessitates distillation for both quality enhancement and safety. The research comprises a two-stage distillation, featuring 11 temperature variations (100-150°C) in the first stage and 9 variations (75-155°C) in the second stage. Characterization involves pH assessment and Gas Chromatography-Mass Spectrometry (GC-MS) analysis to identify chemical components. The pH range in the initial distillation stage spans 1.18-1.30, and the second stage ranges from 1.11-1.39. GC-MS analysis of raw coconut shell liquid smoke reveals 25 components, including phenol, furan, ketone, acid, alcohol, benzenediol and derivatives, alkyl aryl ether, deoxycytidine, and silicone grease. GC-MS evaluation is conducted on products of the first stage at 125 and 135°C, and the second stage products at 145 and 155°C. In the first distillation stage, liquid smoke contains phenol and assorted compounds. Conversely, the second stage yields purer phenol compounds. The findings suggest potential applications of the redistillation product as raw material in food preservation, antiseptics, and insecticides.

Tritordeum, a hybrid cereal with a highly tricin-enriched lignin

The lignin from tritordeum straw, a hybrid cereal from crossbreeding of durum wheat and wild barley, was isolated and chemically characterized. Its composition and structure were studied by analytical pyrolysis (Py-GC/MS), nuclear magnetic resonance spectroscopy (NMR), Derivatization Followed by Reductive Cleavage (DFRC) method, and gel permeation chromatography (GPC). The data revealed an enrichment of guaiacyl (G) units (H:G:S of 3:61:36), which had a significant impact on the distribution of inter-unit linkages. The predominant linkages were the β–O–4′ alkyl-aryl ethers (78 % of all linkages), with substantial proportions of condensed linkages such as phenylcoumarans (11 %), resinols (4 %), spirodienones (4 %), and dibenzodioxocins (2 %). Moreover, DFRC revealed that tridordeum straw lignin was partly acylated at the γ-OH with both acetates and p-coumarates. Acetates were principally attached to G-units, whereas p-coumarates were predominantly attached to S-units. Furthermore, and more importantly, tritordeum lignin incorporates remarkable amounts of a valuable flavone, tricin, exceeding 30 g per kilogram of straw. Given the diverse industrial applications associated with this high-value molecule, tritordeum straw emerges as a promising and sustainable resource for its extraction.

Synthesis of Zinc Oxide Nanoparticles using Extract of Cynodon dactylon and Assessment of their Biological Activity against Staphylococcus aureus and Escherichia coli

Nanotechnology is a groundbreaking technology that that has been widely applied in creating materials which are useful in various fields. It's important to maintain eco-friendly approaches for synthesis of nanoparticles by diversifying the substrate sources. In this study, the researchers used aqueous extract of Cynodon dactylon to synthesize zinc oxide nanoparticles (ZnONPs). Quantitative phytochemical analysis of the extract showed high concentrations of alkaloids, flavonoids, carbohydrates, proteins, amino acids, and phenolic compounds. In contrast, moderate concentrations of tannins, oils, and fats, and low concentrations of phlorotannins, saponin, triterpenoids, and cardiac glycosides were found. Sterols, anthraquinone glycosides, gums, and mucilages were not detected in the extract. The synthesized ZnONPs showed absorbance ranging from 293 nm to 336 nm, with a peak at 307 nm. Fourier transform infrared (FTIR) spectroscopy revealed that the surface of the ZnONPs contained alcohol (intermolecular bonded), alkyne, amine salt, alkane, alkyne, aromatic compounds, conjugated alkene, amine, nitro compound, sulfonyl chloride, alkylaryl ether, and sulfoxide. Dynamic light scatering (DLS) analysis of the ZnONPs showed that its average size was 35.34±1.64 nm, and the polydispersity index was 0.6335. Spectrum of X ray diffraction indicated that peaks formed at 2θ and their corresponding orientation planes are 31.92o (100), 34.62o (002), 36.44o (101), 47.64o (102), 56.84o (110), 63.3o (200), and 68.16o (112). Transmission electron micrograph revealed the spherical shape, and nonuniform sizes of ZnONPs, which ranged from 0.52 nm to 8.32 nm. Antibacterial analysis of biosynthesized ZnONPs recorded 16±3.2 mm and 6.0±2.2 mm; 6.7±2.1 mm and 4.33±1.3 mm, 0.0±0.0 mm and 1.0±1.41 mm, against Staphylococcus aureus and Escherichia coli, at 53.3 mg/mL, 26.7 mg/mL and 13.3 mg/ml concentrations, respectively. At sub-inhibitory concentrations, biosynthesized ZnONPs demonstrated effective dose-dependent antibiofilm formation activity against E. coli and S. aureus. Consequently, extract of Cynodon dactylon is suitable for biosynthesis of ZnONPs with effective antibacterial and antibiofilm formation activities.

Synthesis of Alkyl Aryl Ethers by O-Arylation of Alcohols with Diaryliodonium Salts: Scope, Limitations, and Mechanism

AbstractWe describe the development of a C–O coupling reaction between aryl(2,4,6-trimethoxyphenyl)iodonium salts and aliphatic alcohols under weak base conditions. The scope of the reaction is presented, with 16 examples ranging in yield from moderate to high (54–96%). The limitations of the reaction are also presented. Mechanistic experiments reveal a complex network of reactions that include side reactions that generate arynes and oxidize the alcohol nucleophile.

Bioethanol lignin-rich residue from olive stones for electrospun nanostructures development and castor oil structuring

This work describes the chemical and structural characterization of a lignin-rich residue from the bioethanol production of olive stones and its use for nanostructures development by electrospinning and castor oil structuring. The olive stones were treated by sequential acid/steam explosion pretreatment, further pre-saccharification using a hydrolytic enzyme, and simultaneous saccharification and fermentation (PSSF). The chemical composition of olive stone lignin-rich residue (OSL) was evaluated by standard analytical methods, showing a high lignin content (81.3 %). Moreover, the structural properties were determined by Fourier-transform infrared spectroscopy, nuclear magnetic resonance, and size exclusion chromatography. OSL showed a predominance of β-β′ resinol, followed by β-O-4′ alkyl aryl ethers and β-5′ phenylcoumaran substructures, high molecular weight, and low S/G ratio. Subsequently, electrospun nanostructures were obtained from solutions containing 20 wt% OSL and cellulose triacetate with variable weight ratios in N, N-Dimethylformamide/Acetone blends and characterized by scanning electron microscopy. Their morphologies were highly dependent on the rheological properties of polymeric solutions. Gel-like dispersions can be obtained by dispersing the electrospun OSL/CT bead nanofibers and uniform nanofiber mats in castor oil. The rheological properties were influenced by the membrane concentration and the OSL:CT weight ratio, as well as the morphology of the electrospun nanostructures.

Elucidation of bioactivity of tricin released by thioacidolysis from wheat straw lignin

Tricin is a complex compound with chemical bonds to phenylpropane units of lignin in gramineous plants, and it is predominantly bound to lignin by β-O-4 ether bonds. Thioacidolysis cleaves the alkyl aryl ether bonds, which releases tricin from the tricin-lignin complex and maintains the natural structure of the tricin. In this study, milled wood lignin (MWL) was isolated from wheat straw by Bjӧrkman’s method, and the MWL was subjected to thioacidolysis to release tricin from the MWL. Medium-pressure preparative liquid chromatography was used for further purification. FT-IR and 1H-NMR analyses showed that the purified fraction was composed mainly of tricin-type flavonoids. The extracted tricin had strong scavenging capacity against 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radicals, with a half maximal inhibitory concentration (IC50) of 51.9 mg/L. Drug sensitivity paper testing showed that the extracted tricin inhibited the growth of Escherichia coli. The bacteriostatic circle diameters of tricin from wheat straw MWL and quercetin standard were 9.17 and 7.52 mm, respectively. A 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay showed that the tricin from wheat straw MWL had possible inhibitory effect on lung cancer A549 cells, with a maximum inhibitory performance of 44.5%.

A novel vardenafil analog in a healthcare product: Preparation, characterization, and quantification

Objective: This study is aimed to develop a qualitative and quantitative method to detect a novel vardenafil analogue from a healthcare product, which is claimed to enhance sexual function. Method: The unknown compound was detected by non-targeted screening using ultra-high performance liquid chromatography-quadrupole-time-of-flight mass spectrometry (UPLC-Q-TOF-MS). MS2 spectra showed that the characteristic fragment ions of this unknown compound were highly similar to those of vardenafil. This compound was subsequently isolated by silica gel column chromatography and characterized by 1D (dimension) and 2D nuclear magnet resonance (NMR) specta, ultra-violet (UV) spectra, and fourier transform infrared (IR) spectra. A quantitative method for analyzing this identified compound in various healthcare product was developed based on high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS).Results: The unknown compound was identified as 2-(5-((4-ethylpiperazin-1-yl)sulfonyl)-2-propoxyphenyl)-5-methyl-7-propylimidazo.[5,1-f] [1,2,4]triazin-4(3H)-one based on the spectroscopic data. Quantitative results revealed that the matrix calibration curves of this compound had a good linear ranges of 2～50 ng/mL in pressed candy (R2 = 0.998), energy coffee (R2 = 0.999), and health wine (R2 = 0.997), respectively. The matrix effects, recoveries, and limit of quantitation (LOQ) of this compound all met the requirements of quantitative validation. Finally, the content of this compound in 5 batches of positive samples ranged from 1.24 to 7.20 g/kg. Conclusion: This study identified a novel vardenafil analog from a healthcare product and named it O-propyl vardenafil, and this compound was distinguished from vardenafil by the replacement of the ethyl group with a propyl group at the aryl alkyl ether moiety. Our developed quantitative method could meet practical needs. The high positive rate (16.67%) in 30 samples suggested that the related regulators should be alert to O-propyl vardenafil in routine test since it has not been detected ever before.

Assessment of functional group in herbal formulation sathakuppai chooranam through fourier transform infrared spectroscopy

Background: The Sathakuppai chooranam is a single herbal medicine used in the treatment of Kumbavatham (Periarthritis). Objective: This study is aimed to evaluating the morphology and elemental charecterization of the Sathakuppai chooranam. Materials and methods: The ingredients were collected and purified and the drug was prepared as per Siddha literature Siddha Vaithiya Pathartha Guna vilakkam. It is subjected into characterisation through FT-IR analysis. Results: The FT-IR characterization showed the presence of functional groups like O-H stretching (carboxylic acid, alcohol molecule), N-H stretching (amine salt),C-H stretching (alkene), N-H stretching (amine salt), C-H stretching (alkene),C=C stretching (conjugate alkene, cyclic alkene,alpha beta unsaturated ketone), N=H bending (amine),O-H bending (carboxylic acid, alcohol),C-O stretching (alkyl aryl ether, primary alcohol), C-N stretching (amine), S=O stretching (sulfoxide), C=C bending (alkene), C-Br stretching (halo compund)which ensures the therapeutic effect of drug. Conclusion: The instrumental analysis FT-IR study for Sathakuppai chooranam shows the presence of functional groups through the stretch and bends which is responsible for its functional activity. The functional groups present in Sathakuppai Chooranam have analgesic, anti-inflammatory activities. This will ensure the efficacy and therapeutic effect of Sathakuppai Chooranam. This study forms the base for the pharmaceutical analysis of the Sathakuppai Chooranam.

Ring Opening of Aziridines by Pendant Silanols Allows for Stereospecific Preparations of 1'-Amino-tetrahydrofurans.

We have developed a highly stereospecific cyclization of aziridine silanols into 1'-amino-tetrahydrofurans. Our protocol of stirring a substrate with 10 mol % Sc (OTf)3 and 1 equivalent of NaHCO3 in CH2Cl2 is mild and compatible with a range of activating aziridine N-substituents (including tosylates, mesylates, and carbamates) and functional groups on the alkyl chains (including substituted aryl rings, alkyl bromides, and alkyl ethers). In all cases examined, trans di-substituted aziridine silanols give products with an erythro configuration; conversely, cis di-substituted aziridine silanols give products with a threo configuration. While literature syntheses of 1'-amino-tetrahydrofurans exist, only one example, contemporaneous with our work, uses a similar cyclization for their construction. Control experiments demonstrate that, for this transformation, the silanol is not particularly privileged, and a variety of protecting groups on the alcohol (including other silicon protecting groups, benzyl ethers, and MOM ethers) are compatible with product formation.

Ultrasound‐Mediated Monodesulfonation of Polyphenol Sulfonate and One‐Pot Generation of Alkyl Aryl Ether under Solvent‐Free Conditions

AbstractAn effective approach for monodesulfonation of polyphenol sulfonate under ultrasonic irradiation was reported. Series of substituted ortho‐, meta‐ or para‐hydroxylphenol sulfonates or 5‐hydroxy‐1,3‐phenylene bis(4‐methylbenzenesulfonate) were obtained specifically in the presence of sodium hydroxide in acetonitrile. With treatment of potassium carbonate in alcohol, alkyloxylphenol sulfonates was provided via one‐pot monodesulfanation followed by alkylation under ultrasonicated solvent‐free conditions. The alcohol had been regarded as green alkylation reagent. The results of the exploration of the scalability of monodesulfonation and one‐pot monodesulfonation‐alkylation of resorcinol bissulfonate indicated that such modes had the potential application value in scale production.

Unveiling lignin structures and lignin-carbohydrate complex (LCC) linkages of bamboo (Phyllostachys pubescens) fibers and parenchyma cells

Bamboo (Phyllostachys pubescens) is an attractive biomass block to develop biorefining industry, however, less emphasis has been placed on elucidating the chemical linkage variations of lignin and LCC between different bamboo cell walls. Here, purified milled wood lignin (MWLp) and lignin-carbohydrate complex (LCC) were isolated from bamboo (Phyllostachys pubescens) fibers (BF) and parenchyma cells (PC), respectively. The variations of structure features and chemical linkages of lignin and LCC were investigated via FT-IR, 2D HSQC NMR, and 31P NMR techniques. 2D HSQC NMR revealed that β-O-4 alkyl-aryl ether linkages and resinol (β-β) substructure were the main substructures in BF-MWLp and PC-MWLp. β-1 linkages existed in the PC-MWLp (3.18/100 Ar), but not in BF-MWLp. Moreover, tricin, as a flavonoid compound, was only detected in the BF-MWLp. The amount of the syringyl (S) units of PC-MWLp was higher than BF-MWLp. The results indicated that phenyl glycoside (PhGlc) bonds (mainly lignin and xylan) were the predominant chemical linkage type of LCC bonds in BF-LCC and PC-LCC, and the high contents of PhGlc bonds (45.53/100 Ar) were presented in PC. Our finding can provide a reference for the structural variations of lignin and LCC between the different bamboo cell walls.