Multiscale structure changes and mechanism of polyphenol-amylose complexes modulated by polyphenolic structures.

This study was designed to investigate the effect of polyphenolic structure on the interaction strength and process between polyphenols (gallic acid (GA), epigallocatechin gallate (EGCG) and tannic acid (TA)) and amylose (AM). The results of Fourier transform infrared spectroscopy, isothermal titration calorimetry, X-ray photoelectron spectroscopy and molecular dynamic simulation (MD) suggested that the interactions between the three polyphenols and AM were noncovalent, spontaneous, low-energy and driven by enthalpy, which would be enhanced with increasing amounts of pyrogallol groups in the polyphenols. The results of turbidity, particle size and appearance of the complex solution showed that the interaction process between polyphenols and AM could be divided into three steps and would be advanced by increasing the number of pyrogallol groups in the polyphenols. At the same time, MD was intuitively employed to exhibit the interaction process between amylose and polyphenols, and it revealed that the interaction induced the aggregation of amylose and that the agglomeration degree of amylose increased with increasing number of pyrogallol groups at polyphenols. Last, the SEM and TGA results showed that TA/AM complexes had the tightest structure and the highest thermal stability (TA/AM˃EGCG/AM˃GA/AM), which could be attributed to TA having five pyrogallol groups.

Oligomerization Mechanisms of Tea Catechins Involved in the Production of Black Tea Thearubigins.

Thearubigins (TRs) are chemically ill-defined black tea pigments composed of numerous catechin oxidation products. TRs contain oligomeric components; however, the oligomerization mechanisms are poorly understood. The comparison of the 13C nuclear magnetic resonance (NMR) spectra of TRs with different molecular sizes suggested the participation of A-ring methine carbons in the oligomerization. Crushing fresh tea leaves with phloroglucinol, a mimic of the catechin A-rings, yielded the phloroglucinol adducts of the B-ring quinones of pyrogallol-type catechins and dehydrotheasinensins, indicating that intermolecular oxidative couplings between pyrogallol-type B-rings and A-rings are involved in the oligomerization. This is supported by the comparison of the 13C NMR spectra of the oligomers generated from the dehydrotheasinensins and epicatechin. Furthermore, the presence of the quinones or related structures in the catechin oligomers is shown by condensation with 1,2-phenylenediamine. The pyrogallol-type catechins account for approximately 70% of tea catechins; therefore, the B-A ring couplings of the pyrogallol-type catechins are important in the catechin oligomerization involved in TR production.

Accelerated Wound Healing with a Diminutive Scar through Cocrystal Engineered Curcumin.

Pharmaceutical cocrystals ( Regulatory Classification of Pharmaceutical Co-Crystals Guidance for Industry; Food and Drug Administration, 2018) are crystalline solids produced through supramolecular chemistry to modulate the physicochemical properties of active pharmaceutical ingredients (APIs). Despite their extensive development in interdisciplinary sciences, this is a pioneering study on the efficacy of pharmaceutical cocrystals in wound healing and scar reducing. Curcumin-pyrogallol cocrystal (CUR-PYR) was accordingly cherry-picked since its superior physicochemical properties adequately compensate for limitative drawbacks of curcumin (CUR). CUR-PYR has been synthesized by a liquid-assisted grinding (LAG) method and characterized via FT-IR, DSC, and PXRD analyses. In vitro antibacterial study indicated that CUR-PYR cocrystal, CUR+PYR physical mixture (PM), and PYR are more effective against both Gram-negative (Pseudomonas aeruginosa and Escherichia coli) and Gram-positive (Staphylococcus aureus and Bacillus subtilis) bacteria in comparison with CUR. In vitro results also demonstrated that the viability of HDF and NIH-3T3 cells treated with CUR-PYR were improved more than those received CUR which is attributed to the effect of PYR in the form of cocrystal. The wound healing process has been monitored through a 15 day in vivo experiment on 75 male rats stratified into six groups: five groups treated by CUR-PYR+Vaseline (CUR-PYR.ung), CUR+PYR+Vaseline (CUR+PYR.ung), CUR+Vaseline (CUR.ung), PYR+Vaseline (PYR.ung), and Vaseline (VAS) ointments and a negative control group of 0.9% sodium chloride solution (NS). It was revealed that the wounds under CUR-PYR.ung treatment closed by day 12 postsurgery, while the wounds in other groups failed to reach the complete closure end point until the end of the experiment. Surprisingly, a diminutive scar (3.89 ± 0.97% of initial wound size) was observed in the CUR-PYR.ung treated wounds by day 15 after injury, followed by corresponding values for PYR.ung (12.08 ± 2.75%), CUR+PYR.ung (13.89 ± 5.02%), CUR.ung (16.24 ± 6.39%), VAS (18.97 ± 6.89%), and NS (20.33 ± 5.77%). Besides, investigating histopathological parameters including inflammation, granulation tissue, re-epithelialization, and collagen deposition signified outstandingly higher ability of CUR-PYR cocrystal in wound healing than either of its two constituents separately or their simple PM. It was concluded that desired solubility of the prepared cocrystal was essentially responsible for accelerating wound closure and promoting tissue regeneration which yielded minimal scarring. This prototype research suggests a promising application of pharmaceutical cocrystals for the purpose of wound healing.

Laponite stabilized endogenous antibacterial hydrogel as wet-tissue adhesive.

Clinical adhesives for suture-less wound closure remain the problem of poor biocompatibility, weak adhesive strength, and no endogenous antibacterial ability. Here, we designed a novel antibacterial hydrogel (CP-Lap hydrogel) consisting of chitosan and ε-polylysine after being modified with gallic acid (pyrogallol structure). The hydrogel was crosslinked by glutaraldehyde and Laponite via Schiff base and dynamic Laponite-pyrogallol interaction, free from heavy metal and oxidants. Given its dual crosslinking feature, the CP-Lap hydrogel exhibited adequate mechanical strength (150-240 kPa) and demonstrated swelling and degradation resistance. For a typical lap shear test with pigskin, the apparent adhesion strength of the CP-Lap hydrogel could be enhanced to ∼30 kPa benefiting from the O2 blocking effect provided by nanoconfinement space between Laponite. In addition, the hydrogel showed effective antibacterial properties and excellent biocompatibility. The results indicated that this hydrogel has great potential for wound-closing bioadhesives to avoid chronic infections and further harm.

Synthesis of biologically derived poly(pyrogallol) nanofibers for antibacterial applications.

Herein, we present the facile synthesis of poly(pyrogallol) biopolymers and their application as antibacterial agents. Pyrogallol is a class of phenolic compounds that can be found in various plants. Polymerization was performed by the auto-oxidation of pyrogallol under a hydrated condition. The microscopic image of poly(pyrogallol) shows a highly homogenous nanofibrous structure with a diameter of 100.3 ± 16.3 nm. Spectroscopic analysis by FT-IR spectroscopy, Raman spectroscopy, and XPS corroborated the formation of ether (C-O-C) bonds between the hydroxyl group and adjacent carbons of pyrogallol during polymerization. The FT-IR and XPS spectra also revealed redox-active gallol functional groups on poly(pyrogallol) nanofibers, which can be used to release free electrons and protons during oxidation followed by the generation of reactive oxygen species (ROS). The generated ROS from poly(pyrogallol) was used to inhibit the growth of bacteria, Escherichia coli, at a inhibition rates of 56.3 ± 9.7% and 95.5 ± 2.0% within 0.5 and 2 h, respectively. This finding suggests that poly(pyrogallol) can be used as a naturally occurring antibacterial agent for various biomedical and environmental applications.

Adhesion and Cohesion Differences between Catechol- and Pyrogallol-Functionalized Chitosan.

Marine-inspired phenolic compounds that exhibit underwater adhesion are used as biomedical adhesives under wet conditions. While these applications mainly use catechol and pyrogallol moieties that contain different numbers of hydroxyl groups on their benzene rings, how this difference affects adhesion and cohesion is not well understood. Herein, the chitosan backbone is functionalized with catechol and pyrogallol at similar modification rates (to give chitosan-catechol (CS-CA) and chitosan-pyrogallol (CS-GA), respectively) and their interaction energies are compared by using a surface forces apparatus (SFA). The phenolic moieties decrease the rigidity of the chitosan chain and increase solubility; consequently, CS-CA and CS-GA are more cohesive and adhesive than chitosan at pH 7.4. Moreover, the additional hydroxyl group of GA provides a further interacting chance; hence, CS-GA is more cohesive and adhesive than CS-CA. This study provides in-depth insight into interactions involving chitosan derivatives bearing introduced phenolic moieties that will help to develop biomedical adhesives.

Diffusion NMR Reveals the Structures of the Molecular Aggregates of Resorcin[4]arenes and Pyrogallol[4]arenes in Aromatic and Chlorinated Solvents.

The hexameric assemblies of resorcinarenes and pyrogallolarenes are fascinating structures that can serve as nanoreactors in which new chemistry and catalysis occur. Recently, it was suggested based on SANS or SAXS that C11-resorcin[4]arene (1) forms octameric aggregates of a micellar rather than capsular structure in toluene. Here, using NMR spectroscopy, diffusion NMR, and DOSY performed on solutions of C11-resorcin[4]arene (1), C11-pyrogallol[4]arene (2), and mixtures thereof in protonated and deuterated solvents, we found that, in benzene and toluene, 1 primarily formed hexameric capsules accompanied by a minor product with diffusion characteristics consistent with an octameric assembly. In chloroform, 1 formed hexameric capsules. In toluene, 2D NMR revealed two populations of encapsulated toluene molecules in the same capsule of 1. The addition of tetrahexylammonium bromide to the assemblies of 1 in aromatic solvents drove the equilibrium toward the formation of the hexameric capsules. Interestingly, 2 formed only hexameric capsules in all solvents tested.

Rapid fabrication of bionic pyrogallol-based self-adhesive hydrogel with mechanically tunable, self-healing, antibacterial, wound healing, and hemostatic properties.

Hydrogels are functional materials that are similar to human skin and have received much attention in recent years for biomedical applications. However, the preparation of nontoxic, highly adhesive, and antimicrobial hydrogels in an efficient way remains a great challenge. Inspired by adhesive mussel foot proteins (mfps) which consist of abundant catecholic amino acids and lysine (Lys) residues, gallic acid-modified ε-poly-L-lysine (EPL/GA) was synthesized, and an active functional monomer (AA-EPL/GA) was then created through a reaction with acrylic acid (AA). The polymerization of AA-EPL/GA occurred rapidly (30-160 s) under blue light (λ = 405 nm) irradiation to produce a biomimetic PAA-EPL/GA hydrogel under mild conditions. The biomimetic pyrogallol-Lys distribution endowed the PAA-EPL/GA hydrogels with superior adhesion in humid environments (with an adhesive strength of 50.02 kPa toward wet porcine skin) and tunable mechanical and self-healing properties. Additionally, the PAA-EPL/GA hydrogels exhibited outstanding antibacterial ability due to the inherent characteristics of GA and EPL. In a mouse model, PAA-EPL/GA adhered firmly around the wound tissues. Photographs of the wound and the histological results demonstrated the ability of the hydrogel to promote wound healing, control wound infection, and suppress scar formation. Moreover, the hydrogel had a good hemostatic effect on liver bleeding. Our results highlighted the promising application potential of GA-based hydrogels, which were easily, harmlessly, and efficiently fabricated by blue light irradiation.

Anion-Based Self-assembly of Resorcin[4]arenes and Pyrogallol[4]arenes.

Spatial sequestration of molecules is a prerequisite for the complexity of biological systems, enabling the occurrence of numerous, often non-compatible chemical reactions and processes in one cell at the same time. Inspired by this compartmentalization concept, chemists design and synthesize artificial nanocontainers (capsules and cages) and use them to mimic the biological complexity and for new applications in recognition, separation, and catalysis. Here, we report the formation of large closed-shell species by interactions of well-known polyphenolic macrocycles with anions. It has been known since many years that C-alkyl resorcin[4]arenes (R4C) and C-alkyl pyrogallol[4]arenes (P4C) narcissistically self-assemble in nonpolar solvents to form hydrogen-bonded capsules. Here, we show a new interaction model that additionally involves anions as interacting partners and leads to even larger capsular species. Diffusion-ordered spectroscopy and titration experiments indicate that the anion-sealed species have a diameter of >26 Å and suggest stoichiometry (M)6(X-)24 and tight ion pairing with cations. This self-assembly is effective in a nonpolar environment (THF and benzene but not in chloroform), however, requires initiation by mechanochemistry (dry milling) in the case of non-compatible solubility. Notably, it is common among various polyphenolic macrocycles (M) having diverse geometries and various conformational lability.

A novel design of multiple ligands for ultrasensitive colorimetric chemosensor of glutathione in plasma sample.

In this study, we developed a novel colorimetric chemosensor for selective and sensitive recognition of Glutathione (GSH) using a simple binary mixture of commercially accessible and inexpensive metal receptors with names, Bromo Pyrogallol Red (BPR) and Xylenol Orange (XO). This procedure is based on the synergistic coordination of BPR and XO with cerium ion (Ce3+) for the recognition of GSH over other available competitive amino acids (AAs) especially thiol species in aqueous media. Generally, cysteine (Cys) and homocysteine (hCys) can seriously interfere with the detection of GSH among common biological species because they possess similar chemical behavior. Using all the information from 1HNMR and FT-IR studies, the proposed interaction is presented in which GSH acts as a tri-dentate ligand with three N donor atoms in conjunction with BPR and XO as mono and bi-dentate ligands respectively. This approach opens a path for selective detection of other AAs by argumentatively selecting the ensemble of mixed organic ligands from commercially available reagents, thereby eliminating the need for developing synthetic receptors, sample preparation, organic solvent mixtures, and expensive equipment. Evaluating the feasibility of the existing method was led to the determination of GSH in human plasma samples.

Lignin-Derived Syringol and Acetosyringone from Palm Bunch Using Heterogeneous Oxidative Depolymerization over Mixed Metal Oxide Catalysts under Microwave Heating.

Biomass valorization to building block chemicals in food and pharmaceutical industries has tremendously gained attention. To produce monophenolic compounds from palm empty fruit bunch (EFB), EFB was subjected to alkaline hydrothermal extraction using NaOH or K2CO3 as a promotor. Subsequently, EFB-derived lignin was subjected to an oxidative depolymerization using Cu(II) and Fe(III) mixed metal oxides catalyst supported on γ-Al2O3 or SiO2 as the catalyst in the presence of hydrogen peroxide. The highest percentage of total phenolic compounds of 63.87 wt% was obtained from microwave-induced oxidative degradation of K2CO3 extracted lignin catalyzed by Cu-Fe/SiO2 catalyst. Main products from the aforementioned condition included 27.29 wt% of 2,4-di-tert-butylphenol, 19.21 wt% of syringol, 9.36 wt% of acetosyringone, 3.69 wt% of acetovanillone, 2.16 wt% of syringaldehyde, and 2.16 wt% of vanillin. Although the total phenolic compound from Cu-Fe/Al2O3 catalyst was lower (49.52 wt%) compared with that from Cu-Fe/SiO2 catalyst (63.87 wt%), Cu-Fe/Al2O3 catalyst provided the greater selectivity of main two value-added products, syringol and acetosyrigone, at 54.64% and 23.65%, respectively (78.29% total selectivity of two products) from the NaOH extracted lignin. The findings suggested a promising method for syringol and acetosyringone production from the oxidative heterogeneous lignin depolymerization under low power intensity microwave heating within a short reaction time of 30 min.

Expression and characterization of catechol 1,2-dioxygenase from Oceanimonas marisflavi 102-Na3.

The gene of catechol 1, 2-dioxygenase was identified and cloned from the genome of Oceanimonas marisflavi 102-Na3. The protein was expressed in Escherichia coli BL21 (DE3) and purified to homogeneity of a dimer with molecular mass of 69.2 kDa. The enzyme was highly stable in pH 6.0-9.5 and below 45 °C and exhibited the maximum activity at pH 8.0 and 30 °C. Being the first characterized intradiol dioxygenase from marine bacteria Oceanimonas sp., the enzyme showed catalytic activity for catechol, 3-methylcatechol, 4-methylcatechol, 3-chlorocatechol, 4-chlorocatechol and pyrogallol. For catechol, Km and Vmax were 11.2 µM and 13.4 U/mg of protein, respectively. The enzyme also showed resistance to most of the metal ions, surfactants and organic solvents, being a promising biocatalyst for biodegradation of aromatic compounds in complex environments.

Identification of pyrogallol as a warhead in design of covalent inhibitors for the SARS-CoV-2 3CL protease.

The ongoing pandemic of coronavirus disease 2019 (COVID-19) caused by severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) urgently needs an effective cure. 3CL protease (3CLpro) is a highly conserved cysteine proteinase that is indispensable for coronavirus replication, providing an attractive target for developing broad-spectrum antiviral drugs. Here we describe the discovery of myricetin, a flavonoid found in many food sources, as a non-peptidomimetic and covalent inhibitor of the SARS-CoV-2 3CLpro. Crystal structures of the protease bound with myricetin and its derivatives unexpectedly revealed that the pyrogallol group worked as an electrophile to covalently modify the catalytic cysteine. Kinetic and selectivity characterization together with theoretical calculations comprehensively illustrated the covalent binding mechanism of myricetin with the protease and demonstrated that the pyrogallol can serve as an electrophile warhead. Structure-based optimization of myricetin led to the discovery of derivatives with good antiviral activity and the potential of oral administration. These results provide detailed mechanistic insights into the covalent mode of action by pyrogallol-containing natural products and a template for design of non-peptidomimetic covalent inhibitors against 3CLpros, highlighting the potential of pyrogallol as an alternative warhead in design of targeted covalent ligands.

A tough, adhesive, self-healable, and antibacterial plant-inspired hydrogel based on pyrogallol-borax dynamic cross-linking.

Multifunctional hydrogels that integrate stretchability, adhesion, self-healing, and antibacterial properties may find use in a variety of fields including electronic skin, wound dressings, and wearable devices; however, traditional hydrogels often exhibit short-term adhesiveness, poor mechanical properties, and a lack of antibacterial activity. Herein, a plant-inspired polyacrylamide-soybean protein isolate-pyrogallol/borax (PAM-SPI-P/B) hydrogel has been developed using a facile green method based on dynamic coordination cross-linking between pyrogallol (PG) and borax. The PG-borax dynamic bonds adjusted the network structure of the hydrogels to provide greater structural integrity to the PAM-SPI double network. This hydrogel possessed a high mechanical strength (large elongation up to 760% and compressive strength up to 1.25 MPa at 80% strain), low swelling ratio, and self-healing properties. Inspired by natural polyphenols that contain adhesive molecules, the addition of pyrogallol provided the hydrogel excellent adhesion to various hydrophilic and hydrophobic substrates. And with the inhibition of pyrogallol autoxidation due to the borax protection, the hydrogel showed repeatable and durable adhesion over 20 cycles. The obtained hydrogels also exhibited good antibacterial activities against Escherichia coli and Staphylococcus aureus because they were based on pyrogallol and borax, which have antibacterial properties. Accordingly, we envision that the PAM-SPI-P/B hydrogels have great potential for use in biomimetic tissues and biosensors.

An Improved System to Evaluate Superoxide-Scavenging Effects of Bioflavonoids.

The pyrogallol autoxidation method has been widely utilized to evaluate various antioxidants in antioxidative bioactivities. However, this method is generally not appropriate for estimating the . O2- radical scavenging capacity of bioflavonoids, as it enables bioflavonoids to generate . O2- radical in oxygen-alkaline (pH 8.2) surroundings. In the present study, an improved DMSO (dimethyl sulfoxide) system (pH 7.25, versus pH 8.2 of the pyrogallol autoxidation) was successfully developed to evaluate the . O2- radical scavenging capacity of bioflavonoids by EPR technique and using the spin trapping reagent DMPO (5,5-dimethyl-1-pyrroline-N-oxide). The non-protonic environment supplied by the system promotes the stabilization of the . O2- radical and therefore ensures a much more accurate measurement of . O2- radical scavenging capacity in bioflavonoids if compared to protonic solvents. The results demonstrated that the effects of scavenging . O2- radicals in natural bioflavonoids follows the order: dihydromyricetin>myricetin>quercetin>kaempferol>baicalein>chrysin, which are well associated with numbers of hydroxyl groups attached to their molecular skeletons and/or active H of their configurations. Interestingly, the higher superoxide-anion scavenging effect measured for dihydromyricetin with respect to myricetin is possibly attributed to the fact that dihydromyricetin can be transformed into myricetin in the presence of . O2- radical, resulting from the homolysis of active H donated from C3-H bond of DMY via . O2- radicals.

A Contribution to the Solid State Forms of Bis(demethoxy)curcumin: Co-Crystal Screening and Characterization.

Bis(demethoxy)curcumin (BDMC) is one of the main active components found in turmeric. Major drawbacks for its usage are its low aqueous solubility, and the challenging separation from other curcuminoids present in turmeric. Co-crystallization can be applied to alter the physicochemical properties of BDMC in a desired manner. A co-crystal screening of BDMC with four hydroxybenzenes was carried out using four different methods of co-crystal production: crystallization from solution by slow solvent evaporation (SSE), and rapid solvent removal (RSR), liquid-assisted grinding (LAG), and crystallization from the melt phase. Two co-crystal phases of BDMC were obtained with pyrogallol (PYR), and hydroxyquinol (HYQ). PYR-BDMC co-crystals can be obtained only from the melt, while HYQ-BDMC co-crystals could also be produced by LAG. Both co-crystals possess an equimolar composition and reveal an incongruent melting behavior. Infrared spectroscopy demonstrated the presence of BDMC in the diketo form in the PYR co-crystals, while it is in a more stable keto-enol form in the HYQ co-crystals. Solubility measurements in ethanol and an ethanol-water mixture revealed an increase of solubility in the latter, but a slightly negative effect on ethanol solubility. These results are useful for a prospective development of crystallization-based separation processes of chemical similar substances through co-crystallization.

FTIR analysis of pyrogallol and phytotoxicity-reductive effect against mercury chloride.

Human activities, especially in industry, have contributed to soil contamination with heavy or toxic metals. The objective of this study was to determine the chelating effect and antioxidant activity of pyrogallol, as well as to evaluate its cytoprotective activity in prokaryotic and eukaryotic models, animal and plant, respectively, against toxic mercury chloride action. Antioxidant activity was determined by DPPH where pyrogallol showed considerable action, chelating even iron ions. For the microbiologic activity assays, microdilution was performed to obtain the minimal inhibitory concentration, minimum bactericidal and minimum fungicide concentration, from which the sub-inhibitory concentrations were determined. The product did not conferred cytoprotection to the tested bacteria and fungi. To evaluate plant cytoprotection, Lactuta sativa seeds were used together with the product at a sub-allelopathic concentration with different HgCl2 concentrations. In this case, the tannin conferred cytoprotection to the plant model, allowing the best growth and development of caulicles and radicles, thus preserving tissues necessary for plant survival. From the results, it is observable that pyrogallol possesses cytoprotective action in the eukaryotic plant model, this action being useful as an alternative which favors the growth of plants in contaminated areas, as the recovering of crop fields or reforestation projects.

Antibacterial Mode of Action of the Daucus carota Essential Oil Active Compounds against Campylobacter jejuni and Efflux-Mediated Drug Resistance in Gram-Negative Bacteria.

Today, an alarming rise of bacterial gastroenteritis in humans resulting from consuming Campylobacter-tainted foods is being observed. One of the solutions for mitigating this issue may be the antibacterial activity of essential oils. In the present research, we propose to study the antibacterial activity against Campylobacter and other Gram-negative bacteria of Daucus carota essential oil and its active molecules. In addition, a few chemically synthesized molecules such as (E)-methylisoeugenol, Elemicin, and eugenol were also studied. The results showed that the essential oil itself and its most active component, (E)-methylisoeugenol, exhibited bactericidal effects. Similar effects were detected using purified and chemically synthesized molecules. Also, it was observed that the Daucus carota essential oil and its active molecules affected intracellular potassium and intracellular ATP contents in Campylobacter cells. Inhibition of the membrane bound FOF1-ATPase was also observed. Eventually, for the first time, the efflux mechanism of active molecules of Daucus carota essential oil was also identified in gamma proteobacteria and its specific antibacterial activity against Campylobacter jejuni was associated with the lack of this efflux mechanism in this species.

Role of polyphenols in plant-mediated synthesis of gold nanoparticles: identification of active components and their functional mechanism.

In order to learn the active components and their functional mechanism during the plant-mediated synthesis of gold nanoparticles (GNPs), 16 kinds of plants were randomly selected as research objects, and statistical analysis was used to obtain more universal and systematic results. Polyphenols are proved to have the most prominent effect in both reductive and protective capability among all components. The relationship between polyphenols concentration and the protective and reductive capability was further studied in detail. Pyrogallic acid was used as a substitute for polyphenols to elucidate the functional mechanism. The concentration of polyphenols was found to be a critical factor for the preparation of GNPs, and the synergistic competition between phenolic hydroxyl and carbonyl groups caused by the oxidation of polyphenols could affect the particle size and morphology of GNPs. This work can provide excellent guidance for the controllable synthesis of GNPs via the plant-mediated method.

Experimental Comparative Study of Dynamic Behavior in Solution Phase of C-Tetra(phenyl)resorcin[4]arene and C-Tetra(phenyl)pyrogallol[4]arene.

The synthesis of phenyl-resorcinarenes and pyrogallolarenes is known to produce a conformational mixture of cone and chair isomers. Depending on the synthesis conditions the composition of the conformational mixture is variable; however, the cone conformer is the greatest proportion of phenyl-resorcin[4]arenes and chair conformer of pyrogallol[4]arenes. The experimental evidence suggests that phenyl-substituted resorcinarene and pyrogallolarene exist as a dynamic boat in solution.