Hydroxyl Substituents Research Articles

Resolving Entangled JH-H-Coupling Patterns for Steroidal Structure Determinations by NMR Spectroscopy.

For decades, high-resolution 1H NMR spectroscopy has been routinely utilized to analyze both naturally occurring steroid hormones and synthetic steroids, which play important roles in regulating physiological functions in humans. Because the 1H signals are inevitably superimposed and entangled with various JH–H splitting patterns, such that the individual 1H chemical shift and associated JH–H coupling identities are hardly resolved. Given this, applications of thess information for elucidating steroidal molecular structures and steroid/ligand interactions at the atomic level were largely restricted. To overcome, we devoted to unraveling the entangled JH–H splitting patterns of two similar steroidal compounds having fully unsaturated protons, i.e., androstanolone and epiandrosterone (denoted as 1 and 2, respectively), in which only hydroxyl and ketone substituents attached to C3 and C17 were interchanged. Here we demonstrated that the JH–H values deduced from 1 and 2 are universal and applicable to other steroids, such as testosterone, 3β, 21-dihydroxygregna-5-en-20-one, prednisolone, and estradiol. On the other hand, the 1H chemical shifts may deviate substantially from sample to sample. In this communication, we propose a simple but novel scheme for resolving the complicate JH–H splitting patterns and 1H chemical shifts, aiming for steroidal structure determinations.

Discovery of trans-3,4,4′-trihydroxystilbene as new lead vasorelaxant agent for antihypertensive drug development

AimsThe structure-vasorelaxant activity relationships (SARs) assessment in previous study has found that trans-3,4,4′-trihydroxystilbene (344OH) could potentially act as a vasorelaxing agent with demonstration of over 2-fold maximal relaxation (Rmax) compared to its analogue, resveratrol. The present study focuses on the mechanism of actions and pathways employed by 344OH and compared to its analogue to further speculate the SAR of stilbenoids towards vasorelaxation. Materials and methodsThe 344OH employed in present study was synthesized based on the protocol in previous study. The vascular responses towards the cumulative addition of 344OH were evaluated using in vitro rat aortic rings assays. Key findingsThe pEC50 and Rmax values were found to be 4.33 ± 0.05 and 106 ± 3.99%, respectively. Results showed that the vasorelaxation of 344OH were predominated by G-protein-coupled muscarinic- (M3) and β2-adrenergic receptors, followed by PGI2/AC/cAMP- and NO/sGC/cGMP-dependent pathways. It was also identified that 344OH employed voltage-activated- (Kv), calcium-activated- (Kca) and inwardly-rectifying (Kir) potassium channels and act as an antagonist for both VOCC and IP3R while regulating the action potential in the vasculature. SignificanceThe different position of hydroxyl substituent located in A-ring of the stilbenoid backbone in 344OH compared to resveratrol resulted in a significant difference in mechanistic actions that lead to 344OH's fast-acting and less time-dependent vasorelaxation behaviour. This has substantially increased the potential of 344OH to be developed as an effective antihypertensive drug in future. Present findings further strengthen our inferences where the SARs study approach should be carried out as the mainstream methodology in future drug development research.

C–H activation goes macro

Polymer Chemistry Methods to oxidize carbonhydrogen (C–H) bonds under mild conditions are showing increasing promise in streamlining small-molecule synthesis. Chen et al. report an application tailored instead to a macromolecule: polyethylene. The world's most common plastic has proven hard to tweak without damaging its structural integrity, but a ruthenium porphyrin catalyst is just selective enough to introduce hydroxyl and carbonyl substituents without disrupting the backbone. The oxidized polymers remained mechanically robust while showing improved adhesion properties and wettability by simple latex paint. Chem 7 , P137 (2021).

Study on the Spontaneous Combustion Tendency of Coal Based on Grey Relational and Multiple Regression Analysis.

The correlation between the spontaneous combustion tendency of coal and its properties are of great importance for safety issues, environmental concerns, and economic problems. In this study, the relationship between multiple parameters, different from the previous single parameter, and the spontaneous combustion tendency was analyzed. The comprehensive judgment index (CJI), which indicates the tendency of coal spontaneous combustion, was obtained for samples collected from different mines. The CJI was measured by the cross-point temperature and had a negative correlation with the spontaneous combustion tendency. Physical pore structures and chemical functional groups were characterized based on cryogenic nitrogen adsorption and Fourier transform infrared spectroscopy measurements, respectively. For analyzing the effect of coal properties on the spontaneous combustion tendency, the grey relational grade was determined by the grey relational analysis between the CJI and the pore structures and functional groups of coal. The grey relational grade of the benzene substituent with CJI had a maximum of 0.8642, and the macropores had the minimum, 0.4169. The higher the gray relational grade was, the more relevant the spontaneous combustion tendency was, indicating that the benzene substituent was the most relevant. To better predict the spontaneous combustion tendency, the average pore diameter, hydroxyl, methyl, methylene, and benzene substituent with a high grey relational grade were selected. Finally, the multiple regression prediction model of CJI was established. The R squared coefficient, significance level, F-distribution, t-distribution, collinearity diagnosis, and residual distribution of the model met the requirements. In addition, two coal samples were selected to verify the spontaneous combustion tendency model. The relative errors between the predicted CJI value and the experimental CJI value were 1.42 and 4.25%, respectively. These small relative errors verified the reasonableness and validity of the prediction model.

Influence of the ligand structure on the properties of bidentate salicylaldimine nickel(II) complexes in ethylene oligomerization

Three nickel(II) complexes (C1–C3) bearing diamine-bridged 4-hydroxysalicylaldehyde ligands (L1–L3) were successfully synthesized, and all the compounds were characterized by physicochemical and spectroscopic methods. The influence of the oligomerization parameters on the catalytic properties of complex C2 was systematically investigated. The results showed that oligomerization parameters played an important role in the catalytic properties and the catalytic activity was 19.90 × 104 g/(mol·Ni·h) and the selectivity of C8+ olefins was 60.25% when the precatalyst dosage was 5 μmol, the Al/Ni molar ratio was 500, the temperature was 25 °C, the reaction time was 30 min and the pressure of ethylene was 0.7 MPa. Complexes C1–C3 with different lengths of the bridged group were evaluated for ethylene oligomerization, and the results showed that the length of the alkyl chain in the ligand had little influence on the catalytic properties. Complex C4 based on ethanediamine-bridged salicylaldimine and C5 based on the hyperbranched salicylaldimine in our previous work were also investigated to study the influence of the ligand structure on the catalytic properties. The catalytic activity [31.80 × 104 g/(mol·Ni·h)] and the content of the low-carbon oligomers (70.16%) for complex C4 were higher than complex C2 with hydroxyl substituent in benzene ring. The catalytic activity and the content of the low carbon oligomers for complex C5 were far higher than other four complexes.

Selectivity for Alkynyl or Allenyl Imidamides and Imidates in Copper-Catalyzed Reactions of Terminal 1,3-Diynes and Azides.

Copper-catalyzed reactions of terminal 1,3-diynes with electron-deficient azides to generate either 3-alkynyl or 2,3-dienyl imidamides and imidates are described. The selectivity depends on the diyne substituents and the nucleophile that reacts with the ketenimide intermediate generated from the corresponding triazole precursor. Reactions of 1,3-diynes containing a propargylic acetate afford [3]cumulenyl imidamides, while reactions using methanol as the trapping agent selectively generate 2,3-dienyl imidates. Five-membered heterocycles were obtained from 1,3-diynes containing a homopropargylic hydroxyl or amine substituent.

Timokinon, Timol ve Karvakrolün Antioksidan Aktiviteleri ve Lipit Oksidasyonunu Önleme Kapasiteleri

Fenolik bileşikler bitkisel kaynaklı olup, aromatik halkasında bir veya daha fazla hidroksil grubu içeren bileşiklerdir. Bitki uçucu yağlarında bulunan bu bioaktif komponentler, doğal antioksidan kaynakları olmaları, serbest radikalleri inaktive etmeleri, oksidatif stresi azaltmaları sebepleri ile terapötik ajan olarak kullanılmış, farmasötik, kozmetik ve gıda araştırma alanlarında yer almışlardır. Bu derlemede, gıda endüstrisinde sentetik antioksidanlar yerine kullanılabilecek timokinon, timol ve karvakrol fenolik bileşikleri incelenmiştir. Timokinon, dünya tarihinde çeşitli hayvan ve insan rahatsızlıklarının tedavisinde yüzyıllardır kullanılan Nigella sativa L.’nin ana aktif bileşenidir. Timol ve karvakrol farmokolojide yaygın olarak kullanılan kekik ve türevlerinin ana bileşenleri olarak bilinmektedir. Çeşitli araştırmalarda timokinon, timol ve karvakrolün sahip oldukları antioksidan aktiviteleri ile lipit oksidasyonunu önleme ve oksidasyonun olası etkilerini azaltma potansiyelleri incelendiğinden, bu çalışmada bu konuda yapılan çalışmalar özetlenmiştir.

Semi-synthetic puwainaphycin/minutissamide cyclic lipopeptides with improved antifungal activity and limited cytotoxicity.

Microbial cyclic lipopeptides are an important class of antifungal compounds with applications in pharmacology and biotechnology. However, the cytotoxicity of many cyclic lipopeptides limits their potential as antifungal drugs. Here we present a structure–activity relationship study on the puwainaphycin/minutissamide (PUW/MIN) family of cyclic lipopeptides isolated from cyanobacteria. PUWs/MINs with variable fatty acid chain lengths differed in the dynamic of their cytotoxic effect despite their similar IC50 after 48 hours (2.8 μM for MIN A and 3.2 μM for PUW F). Furthermore, they exhibited different antifungal potency with the lowest MIC values obtained for MIN A and PUW F against the facultative human pathogen Aspergillus fumigatus (37 μM) and the plant pathogen Alternaria alternata (0.6 μM), respectively. We used a Grignard-reaction with alkylmagnesium halides to lengthen the lipopeptide FA moiety as well as the Steglich esterification on the free hydroxyl substituents to prepare semi-synthetic lipopeptide variants possessing multiple fatty acid tails. Cyclic lipopeptides with extended and branched FA tails showed improved strain-specific antifungal activity against A. fumigatus (MIC = 0.5–3.8 μM) and A. alternata (MIC = 0.1–0.5 μM), but with partial retention of the cytotoxic effect (∼10–20 μM). However, lipopeptides with esterified free hydroxyl groups possessed substantially higher antifungal potencies, especially against A. alternata (MIC = 0.2–0.6 μM), and greatly reduced or abolished cytotoxic activity (>20 μM). Our findings pave the way for a generation of semi-synthetic variants of lipopeptides with improved and selective antifungal activities.

The synthesis and cytotoxic activity of derivatives of 4β-hydroxywithanolide E

4β-Hydroxywithanolide E, which can be obtained in large amounts from the Physalis genus, possessed anti-proliferative effects on a variety of human cancer cell lines. For discussing its anti-tumor structure-activity relationship, a series of 4β-hydroxywithanolide E derivatives (1–17) were synthesized and evaluated for their antitumor activity in vitro towards acute promyelocytic leukemia NB4 cell line by the Alarma blue assay. Cytotoxicity data revealed that the enone structure and C-4 hydroxyl substituents of ring A, together with the side chain (C-20–C-28) play an important effect on the cytotoxicity.

Acidity enhancement of α‐carbon of beta diketones via hydroxyl substituents: A density functional theory study

AbstractDensity functional theory method and B3LYP/6‐311++G(d,p) level of theory were used to determine the acidity of α‐carbon in the hydroxyl derivatives of beta diketones in the gas phase. An investigation of acidity strength in the gas phase indicates that α‐carbon of hydroxyl derivatives of beta diketones become stronger acids than the α‐carbon of beta diketone itself as their conjugate bases gain more stability via both enolate and hydrogen bond formation. Natural bond orbital and quantum theory of atoms in molecules analyses also confirm the role of hydrogen bond interactions on increasing the acidity of α‐carbon of hydroxyl derivatives of beta diketones.

Effects of fatty acyl chains on the interfacial rheological behaviors of amino acid surfactants

Amino acid surfactants derived from vegetable oils have attracted significant interest in the scientific community due to their excellent biocompatibility and low environmental impact. Because of the wide variety of vegetable oils, derived N-acyl amino acid surfactants may feature various fatty acyl groups and therefore offer diverse properties. According to the composition of commonly used vegetable oils, three main characteristics of fatty acyl structures, namely fatty acyl chain length, the number of CC bonds, and hydroxyl substituent, were summarized in this paper and a series of N-fatty acyl glycinate surfactants were synthesized. The specific effects of these three structural factors on the surface tension and interfacial rheological properties were systematically studied. In doing so, we found that an increase of fatty acyl chain length enhanced the interfacial activity and intermolecular interactions of N-fatty acyl glycinate surfactants. Thus, glycinate surfactants with longer fatty acyls could generate more compact adsorption films with a higher dilational modulus. The cis CC bonds in oleoyl and linoleoyl chains were found to bend the long hydrophobic tails, which might affect the compact arrangement of surfactant molecules and increased the viscoelasticity of interfacial films. In addition, the hydroxyl group on ricinoleoyl was found to inhibit the close packing of the hydrophobic tails and reduced intermolecular interactions. As a result, more viscoelastic films were formed by sodium N-ricinoleoylglycinate. The obtained results gained insights into the relationships between fatty acyl structural characteristics and the interfacial arrangements of N-acyl amino acid surfactants, which present a theoretical foundation for surfactant design and further application.

Synthesis, biological activity and POM/DFT/docking analyses of annulated pyrano[2,3-d]pyrimidine derivatives: Identification of antibacterial and antitumor pharmacophore sites

New annulated pyrano[2,3-d]pyrimidine derivatives were synthesized with hydroxyl, methoxy, bromine, nitrile and nitro substituents on its skeleton. The correlated electronic effect of substituents on the magnitude of antibacterial activity was noted. The electron donating substituents (namely; 4–OH, 4–OCH3, 4-Br) and electron withdrawing substituents (4-NO2) on phenyl ring in the pyrano[2,3-d]pyrimidine skeleton exerted different influence on its antimicrobial activity against some Gram-positive and Gram-negative bacteria such as Pseudomonas aureus, E. coli, Staphylococcus aureus, Klebsiella pneumonia and Bacillus cereus. All the pyrano[2,3-d]pyrimidines were characterized by spectroscopic analyses. Antibacterial screening revealed that the presence of heteroaryl, cyano and amino groups on pyrano[2,3-d]pyrimidine skeleton increases its penetrating power on the bacterial cell wall so that the product becomes more biologically active. So the the nature of electron withdrawing or electro-donnor Impact of substituents should be taken in consideration in drug design.Hydrolysis of -CRN to amide restored vital Intramolecular interaction like ortho-nitrophenyl and ONOδ-…NHδ+/amide link, offering a crucial template for antibacterial NH, HO-pharmacophore sites, which ultimately elevated innate antimicrobial profiles. POM combinatorial analysis of tangible electronic contributions due to armed annulated pyrano[2,3-d]pyrimidines concluded their broad antimicrobial activity and viable/prominent drug score index through perspective parameters particularly: inter atomic distance/linkers, steric, electronic, polar parameters, and with a different polarising effect of electron donating/withdrawing environments of substituents. Furthermore, an anti-Kinase pharmacophore site (OCNHCO) was evaluated in continuation of the POM investigations. All synthesized products verified fewer side effects than standard streptomycin, but facile implication in selective cancer media (viz. breast or leucemia still needs to be screened).

Quantum chemical study on the ozonolysis mechanism of guaiacol and the structure-reactivity relationship of phenols with hydroxyl, methoxy, and methyl substituents

• Primary ozonides persist long periods in the ozonolysis of guaiacol. • Criegee intermediates mainly transfer to dioxirane-type compounds. • The formation of secondary ozonides is negligible. • Rate constant positively depends on temperature but not sensitive to pressure. • Frontier molecular orbital property determines the selectivity and reactivity. Quantum chemical calculations with the M06-2X method were performed to uncover the ozonolysis mechanism of guaiacol and several hydroxylated, methoxylated, and methylated phenols to improve the understanding of the ozone-induced attenuation of phenolic compounds. The detailed kinetic properties were obtained by the transition state theory (TST) and the Rice − Ramsperger − Kassel − Marcus (RRKM) theory. Results confirm that the primary ozonides originated from guaiacol occupy considerably long retention time than the short-lived primary ozonides formed from vinyl-type compounds in the air. The TST rate constant of guaiacol ozonolysis is calculated with a value of 8.81 × 10 −20 cm 3 molecule −1 s −1 at room temperature. The RRKM results prove that the rate constant is positively dependent on temperature but shows no relation with pressure. The reactivity of substituted phenols exhibits a strong correlation with the ozone affinity of carbon atoms and the orbital energy difference (E L o -H ac ) between the lowest unoccupied molecular orbital of O 3 and the highest occupied molecular orbital of phenols. The substituents can reduce the value of E L o -H ac and improve the phenols' reactivity, especially when they locate at the ortho - and para -position. The substituents also improve the ozone affinity of carbon atoms due to the electron-withdrawing effect. The methyl group delivers a moderate impact on the reactivity compared to hydroxyl and methoxy groups.

Synthesis of azolyl-substituted adamantane derivatives and their coordination compounds

Reactions of adamantylazoles with nucleophiles (water, carbon monoxide, acetonitrile) in sulfuric acid were studied. New bifunctional adamantane derivatives containing one heterocyclic substituent and one hydroxyl or acetamide substituent were synthesized. The coordination compounds of copper(II) and zinc(II) with 1-adamantyl-1,2,4-triazole, 4-adamantylpyrazole, and 4-adamantyl-3,5-dimethylpyrazole were synthesized and structurally characterized. These complexes are first examples of coordination compounds of azolyladamantanes.

Structure and functional properties of active packaging films prepared by incorporating different flavonols into chitosan based matrix

Kaempferol, quercetin and myricetin are typical flavonols that feature different number of hydroxyl substituents at B-ring. In this study, kaempferol, quercetin and myricetin were individually mixed with chitosan (CS) based film matrix to develop active packaging films. Results showed the incorporation of flavonols produced dense inner microstructure by establishing intermolecular hydrogen bonding interactions with film matrix. The addition of flavonols reduced the water vapor permeability, oxygen permeability and UV–vis light transmittance of the films, whereas elevated the tensile strength, elongation at break, 2,2-diphenyl-1-picrylhydrazyl radical scavenging activity and antimicrobial activity of the films. Among all the films, the film containing myricetin showed the highest water vapor and oxygen barrier abilities and mechanical properties. Notably, different films presented distinct flavonol release behaviors in fatty and aqueous food stimulants. Kaempferol was easily released into fatty food stimulant, while myricetin was easily released into aqueous food stimulant. The release behavior of flavonols in different food stimulants greatly affected the antioxidant activity of the films. Our results suggest the structure and functional properties of the films are closely related to the number of hydroxyl substituents at B-ring of flavonols.

SAR Study on Estrogen Receptor α/β Activity of (Iso)flavonoids: Importance of Prenylation, C-Ring (Un)Saturation, and Hydroxyl Substituents.

Many botanicals used for women's health contain estrogenic (iso)flavonoids. The literature suggests that estrogen receptor beta (ERβ) activity can counterbalance estrogen receptor alpha (ERα)-mediated proliferation, thus providing a better safety profile. A structure-activity relationship study of (iso)flavonoids was conducted to identify ERβ-preferential structures, overall estrogenic activity, and ER subtype estrogenic activity of botanicals containing these (iso)flavonoids. Results showed that flavonoids with prenylation on C8 position increased estrogenic activity. C8-prenylated flavonoids with C2-C3 unsaturation resulted in increased ERβ potency and selectivity [e.g., 8-prenylapigenin (8-PA), EC50 (ERβ): 0.0035 ± 0.00040 μM], whereas 4'-methoxy or C3 hydroxy groups reduced activity [e.g., icaritin, EC50 (ERβ): 1.7 ± 0.70 μM]. However, nonprenylated and C2-C3 unsaturated isoflavonoids showed increased ERβ estrogenic activity [e.g., genistein, EC50 (ERβ): 0.0022 ± 0.0004 μM]. Licorice (Glycyrrhiza inflata, [EC50 (ERα): 1.1 ± 0.20; (ERβ): 0.60 ± 0.20 μg/mL], containing 8-PA, and red clover [EC50 (ERα): 1.8 ± 0.20; (ERβ): 0.45 ± 0.10 μg/mL], with genistein, showed ERβ-preferential activity as opposed to hops [EC50 (ERα): 0.030 ± 0.010; (ERβ): 0.50 ± 0.050 μg/mL] and Epimedium sagittatum [EC50 (ERα): 3.2 ± 0.20; (ERβ): 2.5 ± 0.090 μg/mL], containing 8-prenylnaringenin and icaritin, respectively. Botanicals with ERβ-preferential flavonoids could plausibly contribute to ERβ-protective benefits in menopausal women.

Insight into an Oxidative DNA-Cleaving DNAzyme: Multiple Cofactors, the Catalytic Core Map and a Highly Efficient Variant.

SummaryAn oxidative DNA-cleaving DNAzyme (PL) employs a double-cofactor model “X/Cu2+” for catalysis. Herein, we verified that reduced nicotinamide adenine dinucleotide (NADH), flavin mononucleotide, cysteine, dithiothreitol, catechol, resorcinol, hydroquinone, phloroglucinol, o-phenylenediamine, 3,3′,5,5'-tetramethylbenzidine, and hydroxylamine acted as cofactor X. According to their structural similarities or fluorescence property, we further confirmed that reduced nicotinamide adenine dinucleotide phosphate (NADPH), 2-mercaptoethanol, dopamine, chlorogenic acid, resveratrol, and 5-carboxyfluorescein also functioned as cofactor X. Superoxide anions might be the commonality behind these cofactors. We subsequently determined the conservative change of individual nucleotides in the catalytic core under four different cofactor X. The nucleotides A4 and C5 are highly conserved, whereas the conservative levels of other nucleotides are dependent on the types of cofactor X. Moreover, we observed that the minor change in the PL's secondary structure affects electrophoretic mobility. Finally, we characterized a highly efficient variant T3G and converted its double-cofactor NADH/Cu2+ to sole-cofactor NADH.

The reactivity of cinnamic acid derivatives as lignin precursors

Objectives. Cinnamic acid derivatives belong to a large class of phenolic compounds, which are widely distributed in plants and have high potential for use in the medical and industrial fields. They have various useful practical properties, e.g., antioxidant, anti-inflammatory, antiplatelet, and anti-melanogenic properties. Hydroxycinnamic acids are of particular interest as phenylpropanoids, which are the starting compounds of lignin. The aim of this work was to study the electronic structure and analyze the reactivity of the simplest representatives of phenylpropanoids formed during the biosynthesis of the coumaric (p-hydroxycinnamic), caffeic (3,4-dihydroxycinnamic), ferulic (3-methoxy-4-hydroxycinnamic), sinapic (3,5-dimethoxy-4- hydroxycinnamic), and 3,4-dimethoxycinnamic acids. These acids are the biogenetic precursors of most other phenolic compounds (coumarins, melanins, lignins, and flavonoids) and are found in almost all higher plants.Methods.Calculations with full optimization of the geometric parameters were performed using the original Hartree–Fock theory and hybrid density functional method. All calculations were performed using the Firefly program.Results.A comparative quantum chemical calculation of the geometric parameters of hydroxycinnamic acid molecules was conducted via two methods, and the values of the charges on atoms according to Mulliken were determined. It was found that with the addition of hydroxyl and methoxy substituents at the meta and para positions relative to the carboxyl fragment, the electron density shifts toward the benzene ring, and the symmetry of the molecule decreases. Additionally, in these structures, there is π,π-conjugation of the carboxyl fragment of the –СН=СНСООН molecule with the aromatic ring, which significantly affects the geometric configuration of the molecule. The maximum positive charge is concentrated on the C9 atom, while the maximum negative charge is on the oxygen atoms belonging to the methoxy substituents and the hydroxyl group, which confirms the role of oxygen atoms in the chemical transformations of acids.Conclusions.Two different methods were used to calculate the geometric, electronic, and energy parameters and electrophilicity indices of the studied hydroxycinnamic acids in the gas phase. The obtained values were consistent (within the limits of error) with the experimental data as well as the results described in earlier works’ calculations by other methods.

Structural and Energetic Insights on Two Dye Compounds: 1-Acetyl-2-Naphthol and 2-Acetyl-1-Naphthol.

The energy involved in the structural switching of acyl and hydroxyl substituents in the title compounds was evaluated combining experimental and computational studies. Combustion calorimetry and Knudsen effusion techniques were used to determine the enthalpies of formation, in the crystalline state, and of sublimation, respectively. The gas-phase enthalpy of formation of both isomers was derived combining these two experimental data. Concerning the computational study, the G3(MP2)//B3LYP composite method was used to optimize and determine the energy of the isomers in the gaseous state. From a set of hypothetical reactions it has been possible to estimate the gas-phase enthalpy of formation of the title compounds. The good agreement between the experimental and computational gas-phase enthalpies of formation of the 1-acetyl-2-naphthol and 2-acetyl-1-naphthol isomers, provided the confidence for extending the computational study to the 2-acetyl-3-naphthol isomer. The structural rearrangement of the substituents in position 1 and 2 in the naphthalene ring and the energy of the intramolecular hydrogen bond are the factors responsible for the energetic differences exhibited by the isomers. The gas phase tautomeric keto ↔ enol equilibria of the o-acetylnaphthol isomers were analyzed using the Boltzmann’s distribution.

Adsorption of organic pollutants from the aqueous phase using graphite as a model adsorbent

Although graphite is not effective as an adsorbent in water treatment, it provides a homogenous, non-porous, carbonaceous structure that is ideal for studying fundamental adsorption mechanisms. High-purity graphite powder (C content 99.5%) was oxidized in an ozone stream, producing a near-surface oxygen content of 5.9 at.%, and was used together with the virgin material to establish adsorption isotherms for organic compounds in aqueous solutions. We examined how the aromaticity and substituents of the adsorptives affect adsorption on the model-activated carbon surface. For both virgin and oxidized graphite, the adsorption capacity for the aromatic compounds decreased in the order 1-naphthol > 2-methoxynaphthalene > naphthalene > anisole > phenol, with significant differences in the adsorption capacities of the two graphite species observed only for anisole, naphthalene, and 1-naphthol. The Freundlich constants (KF) for the five compounds on virgin graphite were 23.9, 10.3, 5.5, 1.4, and 0.8 (nmol mg−1 )/(µmol L−1) n, respectively. Naphthalene and 1-naphthol were slightly more adsorbed on the virgin material, whereas oxidized graphite had marginally better adsorption properties for anisole. The results underline the importance of dispersive and π– π interactions in the adsorption of organic compounds on carbonaceous adsorbents; a second aromatic ring in 1-naphthol and 2-methoxynaphthalene greatly increased the adsorption capacity for these compounds compared with their one-ring counterparts phenol and anisole. Differences were also observed in the adsorption of compounds containing hydroxyl or methoxy substituents, which have electron-donating properties (a resonance effect) but different electron-withdrawal characteristics (caused by induction). Two amino acids occurring as zwitterions, l-tryptophan and l-tyrosine, were also tested as adsorptives. l-Tryptophan, which has a larger aromatic system, achieved higher loading on graphite, suggesting an adsorption mechanism primarily governed by dispersive and π– π interactions for these two ionic compounds as well.