Hydroxyphenyl Group Research Articles

Understanding the Interplay of the Brønsted Acidity of Catalyst Ancillary Groups and the Solution Components in Iron-porphyrin-Mediated Carbon Dioxide Reduction.

The rapid and efficient conversion of carbon dioxide (CO2) to carbon monoxide (CO) is an ongoing challenge. Catalysts based on iron-porphyrin cores have emerged as excellent electrochemical mediators of the two proton + two electron reduction of CO2 to CO, and many of the design features that promote function are known. Of those design features, the incorporation of Brønsted acids in the second coordination sphere of the iron ion has a significant impact on catalyst turnover kinetics. The Brønsted acids are often in the form of hydroxyphenyl groups. Herein, we explore how the acidity of an ancillary 2-hydroxyphenyl group affects the performance of CO2 reduction electrocatalysts. A series of meso-5,10,15,20-tetraaryl porphyrins were prepared where only the functional group at the 5-meso position has an ionizable proton. A series of cyclic voltammetry (CV) experiments reveal that the complex with -OMe positioned para to the ionizable -OH shows the largest CO2 reduction rate constants in acetonitrile solvent. This is the least acidic -OH of the compounds surveyed. The turnover frequency of the -OMe derivative can be further improved with the addition of 4-trifluoromethylphenol to the solution. In contrast, the iron-porphyrin complex with -CF3 positioned opposite the ionizable -OH shows the smallest CO2 reduction rate constants, and its turnover frequency is less enhanced with the addition of phenols to the reaction solutions. The origin of this effect is rationalized based on kinetic isotope effect experiments and density functional calculations. We conclude that catalysts with weaker internal acids coupled with stronger external acid additives provide superior CO2 reduction kinetics.

A Versatile Passivated Protein‐Adsorption Platform for Rapid Healing of Vascular Stents by Modulating the Microenvironment

AbstractBiodegradable stents have paved the way to treat coronary artery disease. However, rapid reendothelialization is required to solve the problems of mismatched degradation rates, localized inflammation, and insufficient biocompatibility. Herein, a novel passivated protein‐adsorption coating is synthesized by coordination chelation, oxidation, cross‐linking, polymerization, and deposition of dopamine, (‐)‐epigallocatechin gallate (EGCG), and copper ions (Cu2+) using two‐electron oxidation. This coating exhibits hierarchical functionality, that is, at the macroscale, its superhydrophilicity conveys antifouling ability; whereas at the microscale, the active groups (quinone‐, amino‐, hydroxyphenyl groups and aromatic ring) facilitate protein adsorption. Antifouling ability prevents acute thrombosis and inflammation and maintains initial microenvironment stability post‐implantation. The active groups facilitate gradual endothelial cells (ECs) adhesion. Meanwhile, the decomposition of nitric oxide (NO) donors to release NO is catalyzed by Cu2+, and EGCG alleviates or prevents oxidative stress damage, inflammatory responses, thrombosis formation, and excessive smooth muscle cells proliferation in the stent microenvironment. This provides favorable conditions for the rapid and healthy growth of ECs. This study proposes a novel strategy for rapid neointima formation comprising healthy ECs on the surfaces of biodegradable stents by depositing a passivated protein‐adsorption coating (polydopamine/EGCG/Cu), opening new possibilities for the efficient treatment of coronary artery disease.

Passivation protein-adhesion platform promoting stent reendothelialization using two-electron-assisted oxidation of polyphenols

Superhydrophilic surfaces play an important role in nature. Inspired by this, scientists have designed various superhydrophilic materials that are widely used in the field of biomaterials, such as PEG molecular brushes and zwitterionic materials. However, superhydrophilic coatings with only anti-fouling properties do not satisfy the requirements for rapid reendothelialization of cardiovascular stent surfaces. Herein, a novel polyphenol superhydrophilic surface with passivated protein-adsorption properties was developed using two-electron oxidation of dopamine and polyphenols. This coating has a multiscale effects: 1) macroscopically: anti-fouling properties of superhydrophilic; 2) microscopically: protein adhesion properties of active groups (quinone-, amino-, hydroxyphenyl groups and aromatic ring). Polyphenols not only enhance the ability of coating to passivate protein-adsorption, but also make the coating have polyphenol-related biological functions. Therefore, the polyphenol and passivated protein-adsorption platform together maintain the stability of the scaffold microenvironment. This, in turn, provides favorable conditions for the growth of endothelial cells on the scaffold surface. In vivo implantation of the coated stents into the abdominal aorta resulted in uniform and dense endothelial cells covering the surface of the neointima. Moreover, new endothelial cells secreted large amounts of functional endothelial nitric oxide synthase like healthy endothelial cells. These results indicate that the polyphenol superhydrophilic coating potentially resists intra-stent restenosis and promotes surface reendothelialization. Hence, polyphenol superhydrophilic coatings with passivated protein-adsorption properties constructed by two-electron-assisted oxidation are a highly effective and versatile surface-modification strategy for implantable cardiovascular devices.

Sticklac-Derived Natural Compounds Inhibiting RNase H Activity of HIV-1 Reverse Transcriptase.

The emergence of drug-resistant viruses is a serious concern in current chemotherapy for human immunodeficiency virus type-1 (HIV-1) infectious diseases. Hence, antiviral drugs aiming at targets that are different from those of approved drugs are still required, and the RNase H activity of HIV-1 reverse transcriptase is a suitable target. In this study, a search of a series of natural compounds was performed to identify the RNase H inhibitors. Three compounds were found to block the RNase H enzymatic activity. A laccaic acid skeleton was observed in all three natural compounds. A hydroxy phenyl group is connected to an anthraquinone backbone in the skeleton. An acetamido-ethyl, amino-carboxy-ethyl, and amino-ethyl are bound to the phenyl in laccaic acids A, C, and E, respectively. Laccaic acid C showed a 50% inhibitory concentration at 8.1 μM. Laccaic acid C also showed inhibitory activity in a cell-based viral proliferation assay. Binding structures of these three laccaic acids were determined by X-ray crystallographic analysis using a recombinant protein composed of the HIV-1 RNase H domain. Two divalent metal ions were located at the catalytic center in which one carbonyl and two hydroxy groups on the anthraquinone backbone chelated two metal ions. Molecular dynamics simulations were performed to examine the stabilities of the binding structures. Laccaic acid C showed the strongest binding to the catalytic site. These findings will be helpful for the design of potent inhibitors with modification of laccaic acids to enhance the binding affinity.

The Pattern of Hydroxyphenyl-Substitution Influences CO2 Reduction More Strongly than the Number of Hydroxyphenyl Groups in Iron-Porphyrin Electrocatalysts

The Pattern of Hydroxyphenyl-Substitution Influences CO₂ Reduction More Strongly than the Number of Hydroxyphenyl Groups in Iron-Porphyrin Electrocatalysts

N-substituted cyclic phosphoramides as flame-retardant and anti-dripping coatings for PET fabric

Fabric made of polyethylene terephthalate (PET) is a common textile that is widely used in daily life. Its flame retardancy has emerged as a major concern for lowering the risk of fire. As a kind of popular flame retardants, cyclic phosphoramides have been widely applied to improve the flame retardancy of various inflammable materials. To achieve more suitable and effective flame retardants for PET fabric, the fire-safety capabilities of PET fabric coated with various cyclic phosphoramides substituted by siloxane (PDPTP), hydroxyphenyl (DPHBP), and hydroxyethyl (PDNP) groups was explored in this work. All of these chemicals can successfully prevent PET fabric from melting and burning, providing it good flame retardancy and non-dripping performance. LOI values for PET fabrics coated with PDPTP, DPHBP and PDNP increased to 24.6, 25.2, and 30.3% under comparison loadings. These flame-retardant coatings enhanced the char-forming capacity for PET fabric. The residues at 700 °C increased to 26.5 and 27.4% for PDPTP and PDNP coated fabric in N2 atmosphere compared with 2.9% for pure fabric. Peak heat release rate (PHRR) and total heat release (THR) was effectively restrained by 50% and 35%, respectively. Fortunately, these flame-retardant coatings had no detrimental effects on the mechanical characteristics of PET fabric and even enhanced the weft's tensile breaking forces. Apart from DPHBP significantly reducing the fabric's whiteness, the whiteness of PDPTP and PDNP coated PET fabric hardly changed. The effect of cyclic phosphoramides with various substitutions on the flame retardancy of PET fabric is thoroughly discussed in this paper, which might be useful in the development of more effective flame retardants for PET materials.

Hydrogen-bond locked purine chromophores with high photostability for lipid droplets imaging in cells and tissues

Recently, hydrogen-bonding has attracted extensive attention in the design of chromophores. Here, a new class of hydrogen-bond locked purine chromophores (HOPs) were reported by introducing a hydroxyphenyl group into the C(6) position of purine. The intramolecular hydrogen bond plays a dominant role to light up these probes. As a bonus, HOPs show high photostability. Moreover, HOPs exhibit remarkable capability for the specific lipid droplets imaging in living cells with excellent biocompatibility and are also potential for diagnosing fatty liver diseases. These results bring important new insights into the photophysics of the purine-based chromophores and provide a new scaffold with high photostability for bioimaging.

Methyl position affect the fluorescence performance of HBT derivatives for the detection of hypochlorite under alkaline condition

Five fluorescent derivatives of hydroxyphenyl-benzothiazole (HBT) with different methyl positions at the hydroxyphenyl group were synthesized with good yield. Their reactivity and fluorescent response to hypochlorite were carefully studied. It was found that the HBT derivatives with meta-methyl (3-HBT or 5-HBT) showed the highest reactivity to hypochlorite under basic conditions, accompanied by the most efficient fluorescence quenching, whereas HBT derivatives with ortho or para methyl exhibited the least reactivity to hypochlorite. The LUMO and HOMO of 3-HBT were further verified to explain the fluorescence behavior by density functional theory (DFT) calculation. The excellent selectivity of 3-HBT toward hypochlorite against other reactive oxygen species (ROS) was also evaluated under the same conditions. The compounds emit bright green fluorescence in a solid-state, which is convenient for designing sensing devices for hypochlorite in water samples. Thus, the HBT derivatives with meta methyl (3-HBT) were successfully applied to fabricate paper sensors for the quantification of hypochlorite in tap water. Hence, the fluorescent 3-HBT exhibits great promise as a selective and sensitive hypochlorite probe in chemical and biological applications.

Iso-Tellurazolium-N-Phenoxides: A Family of Te···O Chalcogen-Bonding Supramolecular Building Blocks.

Formal substitution of the oxygen atom of an iso-tellurazole N-oxide with deprotonated (ortho, meta, and para)-hydroxyphenyl groups generated molecules that readily aggregate through Te···O chalcogen bonding (ChB) interactions. The molecules undergo autoassociation in solution, as shown by variable temperature (VT) 1H NMR experiments and paralleling the behavior of iso-tellurazole N-oxides. Judicious adjustment of crystallization conditions enabled the isolation of either polymeric or macrocyclic aggregates. Among the latter, the ortho compound assembled a calixarene-like trimer, while the para isomer built a macrocyclic tetramer akin to a molecular square. The Te···O ChB distances in these structures range from 2.13 to 2.17 Å, comparable to those in the structures of iso-tellurazole N-oxides. DFT calculations estimate that the corresponding Te···O ChB energies are between -122 and -195 kJ mol-1 in model dimers and suggest that macrocyclic aggregation enhances these interactions.

Cyclic Phenylmethylsiloxane Oligomers in Municipal Landfills and Their Elimination Mechanisms in Leachate Treatment Processes.

This study investigated some sources and elimination mechanisms of phenylmethylsiloxanes in landfill leachates. During a 20-day leaching experiment for electronic wastes collected from one Chinese landfill, significant release (4.9 ng/L to 1.3 μg/L) of cis-/trans-2,4,6-triphenyl-2,4,6-trimethylcyclotrisiloxanes (cis-P3 and trans-P3) and cis-/trans-2,4,6,8-tetraphenyl-2,4,6,8-tetramethylcyclotetrasiloxanes (cis-P4 and trans-P4a,b,c) in simulated leachates was found. From January 2017 to December 2018, P3 and P4 isomers were detected in raw leachates from active cells [<LOQ-990 ng/L, detection frequency (df) = 67-100%] and closed cells (<LOQ-282 ng/L, df = 2.1-98%) of this landfill. Generally, mean mass loads of total phenylmethylsiloxanes in raw leachates were larger in the summer (380 mg/d) and winter (295 mg/d) for active cells, while they decreased from 36.1 mg/d to <LOQ for closed cells during the entire period. During leachate treatment processes, sorption to sludge was responsible for major removal (64-84%) of phenylmethylsiloxanes, while Fenton treatment accounted for 8.5-25% removal. Simulated Fenton experiments indicated that hydroxylation half-lives of P3 (1.3-1.5 h) and P4 (0.65-0.86 h) were 15-91 times faster than their hydrolysis half-lives (22-59 h, pH 3.5). Furthermore, monohydroxylated P4 isomers with a hydroxyphenyl group had larger (3.2-3.9 times) concentrations than those with a hydroxymethyl group, meaning that a phenyl group may be more likely to be hydroxylated than a methyl group.

Synthesis and devices characterization of pyrazolo[4,3-b] pyridine derivatives containing methoxy and hydroxy phenyl groups

Two pyrazolo[4,3-b] pyridine derivatives namely; 2,3-dihydro-6-(4-methoxyphenyl)-1-methyl-3-oxo-2-phenyl-1H-pyrazolo[4,3-b]pyridine-5-carbonitrile (L1) and 2,3-dihydro-6-(4-hydroxyphenyl)-1-methyl-3-oxo-2-phenyl-1H-pyrazolo[4,3-b]pyridine-5-carbonitrile (L2) were prepared. The thermal analysis showed that the L1 is stable up to 266 °C, whereas L2 is stable up to 376 °C. The L1 and L2 powders were found to have polycrystalline structure in which their lattice parameters and Miller indices were determined. Thin films of L1 and L2 were deposited by thermal evaporation technique. The absorption spectra of the films were measured, from which the optical band gap of L1 and L2 films was estimated as 2.72 and 2.83 eV, respectively. Two devices based on the films of both materials, independently, were deposited onto p-Si single crystal substrates, were fabricated and showed rectification behavior. The current density–voltage (J–V) characteristics of both devices were analyzed in which the diode parameters were determined. The device based on L1 and L2 showed ideality factor of 2.73 and 3.5, respectively. Under illumination condition, the device based on L2 showed photovoltaic properties in which the open circuit voltage and short circuit current were measured as a function of light intensity.

Metal-Free Synthesis of Aryltriphenylphosphonium Bromides by the Reaction of Triphenylphosphine with Aryl Bromides in Refluxing Phenol.

A metal-free synthesis of aryltriphenylphosphonium bromides by the reaction of triphenylphosphine with aryl bromides in refluxing phenol is developed. This reaction tolerates hydroxymethyl, hydroxyphenyl, and carboxyl groups in aryl bromides, allowing to synthesize multifunctional aryltriphenylphosphonium bromides, from which facile access to multifunctional aryldiphenylphosphines and their oxides by hydrolysis and subsequent reduction is exemplified. A two-step addition–elimination mechanism, with the elimination step being a fast step, is also proposed.

Easily-prepared Hydroxy-containing Receptors Recognize Anions in Aqueous Media.

Despite their ready availability, O-H groups have received relatively little attention as anion recognition motifs. Here, we report two simple hydroxy-containing anion receptors that are prepared in two facile steps followed by anion exchange, without the need for chromatographic purification at any stage. These receptors contain a pyridinium bis(amide) motif as well as hydroxyphenyl groups, and bind mono- and divalent anions in 9:1 CD3 CN:D2 O, showing a selectivity preference for sulfate. Notably, a "model" receptor that does not contain hydroxy groups shows only very weak sulfate binding in this competitive solvent mixture. In the solid state, X-ray crystallographic studies show that the receptors tend to form extended assemblies with anions; however, 1 H and DOSY NMR studies as well as molecular dynamics simulations show that only 1:1 complexes are present in solution. Molecular dynamics simulations suggest that one of the receptors suffers from competing intramolecular hydrogen bonding, while another binds partially-hydrated anions, with the receptor's O-H groups forming hydrogen bonds to water molecules within the anion's coordination sphere.

Unexpected Solvent Effect in Electrocatalytic CO2 to CO Conversion Revealed Using Asymmetric Metalloporphyrins.

Rapid and efficient electrochemical CO2 reduction is an ongoing challenge for the production of sustainable fuels and chemicals. In this work, electrochemical CO2 reduction is investigated using metalloporphyrin catalysts (metal = Mn, Fe, Co, Ni, Cu) that feature one hydroxyphenyl group, and three other phenyl groups, in the porphyrin heterocycle (5-(2-hydroxyphenyl)-10,15,20-triphenylporphyrin, TPOH). These complexes, which are minimal versions of related complexes bearing up to eight proton relays, were designed to allow more straightforward determination of the role of the 2-hydroxylphenyl functional group. The iron-substituted version of TPOH supports robust reduction of CO2 in acetonitrile solvent, where carbon monoxide is the only detected product. Addition of weak Brønsted acids (1 M water or 8 mM phenol) gives rise to almost 100-fold enhancement in turnover frequency. Surprisingly, the iron analogue is a poor catalyst when the solvent is changed to dimethylformamide. These results lead to the proposal of a model where the hydroxyphenyl group behaves as a local proton source, a hydrogen bond donor to CO2-bound intermediates, and a hydrogen bonding partner to Brønsted acids. The observations from this model suggest improvements for existing electrocatalytic CO2 reduction systems.

Fluorescence of Hydroxyphenyl-Substituted "Click" Triazoles.

The structural and optical properties of hydroxyphenyl-substituted-1,2,3-triazole molecules ("click" triazoles) are described. "Click" triazoles are prepared from the copper(I)-catalyzed azide-alkyne cycloaddition reactions. The alkyne-derived C4 substituent of a "click" triazole engages in electronic conjugation more effectively with the triazolyl core than the azide-derived N1 substituent. Furthermore, triazolyl group exerts a stronger electron-withdrawing effect on the N1 than the C4 substituent. Therefore, the placement of an electron-donating group at either C4 or N1 position and the presence or the absence of an intramolecular hydrogen bond (HB) have profound influences on the optical properties of these compounds. The reported "click" triazoles have fluorescence quantum yields in the range of 0.1-0.3 and large apparent Stokes shifts (8000-13 000 cm-1) in all tested solvents. Deprotonation of "click" triazoles with a C4 hydroxyphenyl group increases their Stokes shifts; while the opposite (or quenching) occurs to the triazoles with an N1 hydroxyphenyl substituent. For the triazoles that contain intramolecular HBs, neither experimental nor computational results support a model of excited state intramolecular proton transfer (ESIPT). Rather, the excited state internal (or intramolecular) charge transfer (ICT) mechanism is more suitable to explain the fluorescence properties of the hydroxyphenyl-substituted "click" triazoles; specifically, the large Stokes shifts of these compounds.

Synthesis and SAR study of new hydroxy and chloro-substituted 2,4-diphenyl 5H-chromeno[4,3-b]pyridines as selective topoisomerase IIα-targeting anticancer agents

As part of our effort to develop potential topoisomerase IIα (topo IIα) targeting anticancer agents, we systematically designed a new series of hydroxy and chloro-substituted 2,4-diphenyl 5H-chromeno[4,3-b]pyridines. Total eighteen compounds were synthesized and tested for their ability to inhibit the function of topo I and IIα, and proliferation of human breast (T47D), colorectal (HCT15), and cervix (HeLa) cancer cells. Except compound 11, all of the tested compounds displayed selective topo IIα inhibitory activity. Compounds 8–18, 22, 24, and 25 showed excellent topo IIα inhibitory activity than a positive control, etoposide. Most of the compounds appeared to be superior to reference compounds in their antiproliferative activity. Structure-activity relationship (SAR) study has shown that it is better to place the hydroxyphenyl group at the 4-position of the central pyridine for superior topo IIα inhibition and antiproliferative activity. Similarly, the 3′-, or 4′-hydroxyphenyl substitution at the 2- and 4-positon of pyridine ring is important for better activity than 2′-substitution.

Structural, photophysical, and theoretical studies of imidazole-based excited-state intramolecular proton transfer molecules

Imidazole-based excited state intramolecular proton transfer (ESIPT) blue fluorescent molecules, 2-(1-(4-chlorophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Cl) and 2-(1-(4-bromophenyl)-4,5-diphenyl-1H-imidazol-2-yl)phenol (BHPI-Br) were designed and synthesized by Debus-Radziszewski method through a one-pot multicomponent reaction in high yield. The synthesized compounds were fully characterized by 1H NMR, 13C NMR, FT-IR, FT-Raman, GC-Mass, and elemental analysis. The molecular structures in single crystal lattice were studied by X-ray crystallographic analysis. Because of the intramolecular hydrogen bonding, hydroxyphenyl group is planar to the central imidazole ring, while the other phenyl rings gave distorted conformations to the central heterocyclic ring. BHPI-Cl and BHPI-Br molecules showed intense ESIPT fluorescence at 480nm, because the two twisted phenyl rings on 4- and 5-positions have reduced intermolecular interaction between adjacent molecules in each crystal through a head-to-tail packing manner. Quantum chemical calculations of energies were carried out by (TD-)DFT using B3LYP/6-31G(d, p) basis set to predict the electronic absorption spectra of the compounds, and they showed good agreement between the computational and the experimental values. The thermal analyses of the synthesized molecules were also carried out by TGA/DSC method.

Spectroscopic characterization of free-base hydroxy(arylethynyl)porphyrins in acidic and basic media

The addition of arylethynyl groups to the porphyrin macrocycle represents an effective strategy with which to enhance the light-harvesting properties of porphyrins. We now extend this modification to arylethynyl porphyrins with two or four [Formula: see text]-hydroxyphenyl substituents. Arylethynyl porphyrins bearing four, but not two, [Formula: see text]-hydroxyphenyl substituents show evidence of aggregation under acidic conditions. Under basic conditions, deprotonation of the peripheral hydroxyphenyl substituents results in substantially red-shifted spectral features and enhanced absorption in the Q-band region. When the hydroxyphenyl groups are appended to the porphyrin macrocylce via the ethynyl spacers, the spectral shifts observed upon deprotonation are significantly enhanced relative to those observed for hydroxyphenylporphyrins, highlighting the role of expanded conjugation in altering porphyrin photophysics.

Polyesters Containing Chiral Imidazolidinone Salts in Polymer Main Chain: Heterogeneous Organocatalysts for the Asymmetric Diels–Alder Reaction

AbstractNovel main‐chain polyesters functionalized with chiral imidazolidinone salts were successfully synthesized. Polycondensation of a chiral imidazolidinone dimer bearing two hydroxyphenyl groups with selected achiral dicarboxylic acid chlorides followed by the addition of an acid afforded polyesters with chiral imidazolidinone salts incorporated into the polymer main chain. Main‐chain ionic polyesters functionalized with chiral imidazolidinone salts in the polymer main chain were synthesized by the neutralization polymerization of a chiral imidazolidinone dimer with selected aromatic disulfonic acids. These polyesters were used as heterogeneous organocatalysts in the asymmetric Diels–Alder reaction of trans‐cinnamaldehyde and 1,3‐cyclopentadiene. By optimizing the polymer main‐chain structure, enantioselectivity of up to 97 % was achieved, which is higher than that attained using the corresponding monomeric and dimeric chiral imidazolidinone salts. These heterogeneous organocatalysts were easily recovered from the reaction mixture and reused several times without significant loss of the enantioselectivity.

Direct electrochemical measurement of metanephrines in spot urine samples for the diagnosis of phaeochromocytomas

Metanephrines (MNs) were suggested as a potential first-line biochemical index for the diagnosis of phaeochromocytomas (PHEO). In this study, we developed a simple electrochemical method for the quantitative measurement of MNs in spot urine samples. As MNs contain a hydroxyphenyl group, they could be oxidized at a certain potential to quinines, which could be further detected by the differential pulse voltammetry (DPV) method using unmodified screen-printed carbon electrode (SPCE). Meanwhile, the solid phase extraction (SPE) technique was used to eliminate the matrix effect in the samples. Consequently, free MNs from the extracted urine sample were screened in a linear range from 0.25 mg/L to 12.5 mg/L. The lowest limit of quantification (LLOQ) for MNs was 0.25 mg/L and the limit of detection (LOD) was 0.05 mg/L. Both the precisions and recoveries were sufficient for clinical applications. The urine samples from 22 patients with PHEO and 63 controls were analyzed by the proposed method. The area under the ROC curve was 0.981 (95% CI, 0.958–1.000) with the sensitivity of 95.5% and the specificity of 92.4% at the cut-off value of 0.404 mg/L in these urine samples. Overall, the proposed method provides a cost-effective, rapid and simple tool for clinical diagnosis of PHEO.