Ring Oxygen Research Articles

Evidence for supramolecular catalysis in the synthesis of cyclic organic carbonates over zeolite Y impregnated with metal iodides

• Styrene carbonate was produced over zeolite Y impregnated with KI. • The conversion and selectivity increase with the loading of impregnated KI. • Calculations showed the epoxide attack by iodide as the rate-determining step. • Calculations indicated a perfect fit of the transition state inside the zeolite cage. • Results were consistent with an enzyme-like behavior in accelerating the reaction. The reaction of epoxides with CO 2 to afford cyclic organic carbonates was studied over zeolite Y impregnated with metal iodides. The experimental results indicated that formation of styrene carbonate is significantly higher on zeolite Y impregnated with KI compared to KI alone. The conversion and selectivity increase with the loading of impregnated KI on the zeolite, although the epoxide/iodide molar ratio were in the range of 86 to 220, among the highest ever reported for this reaction. A periodical DFT study indicated that metal halides are stabilized upon embedding inside the zeolite Y cavity and interact with the framework counter cations. The theoretical study of the reaction pathway, considering the CO 2 cycloaddition to ethylene oxide as model, indicated that the opening of the epoxide ring is the rate-determining step, in agreement with the experimental results that showed a correlation between conversion and the KI loading. The energy of activation is lower on the zeolite/metal halide systems, explaining the higher activity of the metal halides when embedded within the zeolite cavity. The calculations indicated that the reaction occurs on two opposite framework aluminum sites having the embedded metal halide between them. Whereas the epoxide interacts with the framework counter cation of one site, the metal iodide interacts with the counter cation of an opposite site, providing the perfect alignment for the nucleophilic attack and leading to the preferred geometry for the transition state, which resembles a S N 2 type mechanism, with nucleophilic attack of the iodide occurring on the opposite side of the ring oxygen atom. This remarkable behavior is characteristic of enzymatic reactions and stresses the importance of host-guest supramolecular catalysis occurring on zeolitic systems. Graphical Abstract .

Diverse diterpenoids with α-glucosidase and β-glucuronidase inhibitory activities from Euphorbia milii

Four undescribed regular rosane-type diterpenoids euphominoids M−P and three undescribed rearranged rosane-type diterpenoids euphomilones C-E were isolated from the whole plants of Euphorbia milii Des Moul., along with nine known compounds. Their structures were elucidated by detailed interpretation of the NMR and mass spectroscopy. The absolute configurations were established by single-crystal X-ray diffraction experiments, as well as comparative analyses of calculated and experimental ECD spectra. Euphominoid M featured a highly oxygenated ring A and a rare four-membered oxygen ring while euphomilones C-E possessed 7/5/6 or 5/7/6 fused ring systems, which were rarely occurring in rosane-type diterpenoids. In the in-vitro bioassays, 19-norrosa-1,3,5(10),15-tetraene-2,3-diol and antiquorin showed more potent α-glucosidase inhibitory activity than the positive control acarbose while euphominoid C exhibited significant inhibitory activity against both α-glucosidase and β-glucuronidase. To the best of our knowledge, it was the first time that rosane-type diterpenoids were reported as β-glucuronidase inhibitors.

Torsional chirality and molecular recognition: the homo and heterochiral dimers of thenyl and furfuryl alcohol.

Furfuryl alcohol and thenyl alcohol contain a labile torsional chiral center, producing transiently chiral enantiomers interconverting in the nanosecond time-scale. We explored chiral molecular recognition using the weakly-bound intermolecular dimers of both alcohols, freezing stereomutation. Supersonic jet broadband microwave spectroscopy revealed homo and heterochiral diastereoisomers for each alcohol dimer and the structural characteristics of the clusters. All dimers are primarily stabilized by a moderately intense O-H⋯O hydrogen bond, but differ in the secondary interactions, which introduce additional hydrogen bonds either to the ring oxygen in furfuryl alcohol or to the π ring system in thenyl alcohol. Density-functional calculations (B2PLYP-D3(BJ)/def2-TZVP) show no clear preferences for a particular stereochemistry in the dimers, with relative energies of the order 1-2 kJ mol-1. The study suggests opportunities for the investigation of chiral recognition in molecules with torsional barriers in between transient and permanent interconversion regimes.

Distinctive Cassane Diterpenoids Corroborated Biogenetic Evolutionary Process from Caesalpinia mimosoides with Anti‐renal Fibrosis Activity

Comprehensive SummaryEighteen diterpenoids were isolated from the seeds of Caesalpinia mimosoides, including four extremely infrequent cassane diterpenes, together with nine new and five known structures. Compounds 7 and 8 represent the first examples of cassane diterpenoids fused with a ketone carbonyl and a ternary oxygen ring at C‐4, respectively. Compounds 9 and 10 possess a rare five‐member ring in cassane diterpenes. Intriguingly, these isolated components are a clue to the fact that there are lower and higher levels in the plant secondary metabolites, demonstrating the evolution of secondary metabolism of C. mimosoides. All the isolated compounds were tested for their anti‐renal fibrosis activity against TGF‐β1 induced NRK‐52E cell model. The mRNA levels of fibrosis marker α‐SMA, E‐cadherin, Collagen I were tested by qRT‐PCR. The data showed compounds 6 and 9 exhibited the best anti‐renal fibrosis activity and provided preliminary structure−activity relationships.

New Monoterpenoid Indoles with Osteoclast Activities from Gelsemium elegans.

The well-known toxic medicine Gelsemium elegans is widely and historically used to treat bone fracture and skin ulcers by the folk people of China. Two new monoterpenoid indole alkaloids, gelselegandines D and E, together with the known analogue gelegamine A were isolated from G. elegans. Their structures were elucidated by means of spectroscopic techniques and quantum chemical calculations. All isolated compounds were tested for the effects on RANKL-induced osteoclast formation. Interestingly, gelselegandine E and gelegamine A, respectively, showed significant promoting and inhibitory activities on osteoclastogenesis, while gelselegandine D had no activity under the same concentration. This work suggested the different configurations for the carbons near the C-19/20 oxygen rings of the isolated compounds may be the key active groups on osteoclast formation and provided the evidence for the rationality as the traditional treatment for bone-related diseases of G. elegans.

Innovative Strategies for the Construction of Diverse 1'-Modified C-Nucleoside Derivatives.

Modified C-nucleosides have proven to be enormously successful as chemical probes to understand fundamental biological processes and as small-molecule drugs for cancer and infectious diseases. Historically, the modification of the glycosyl unit has focused on the 2'-, 3'-, and 4'-positions as well as the ribofuranosyl ring oxygen. By contrast, the 1'-position has rarely been studied due to the labile nature of the anomeric position. However, the improved chemical stability of C-nucleosides allows the modification of the 1'-position with substituents not found in conventional N-nucleosides. Herein, we disclose new chemistry for the installation of diverse substituents at the 1'-position of C-nucleosides, including alkyl, alkenyl, difluoromethyl, and fluoromethyl substituents, using the 4-amino-7-(1'-hydroxy-d-ribofuranosyl)pyrrolo[2,1-f][1,2,4]triazine scaffold as a representative purine nucleoside mimetic.

Apnoeic Oxygenation during Simulated Difficult Intubation in Obese Patients: Comparison of Buccal Ring, Adair and Elwyn Tube Versus Nasal Cannula: A Prospective Randomized Controlled Trial.

Background:Apnoeic oxygenation is an established method of increasing safe apnoea times during intubation and this is of more importance in obese patients. The usefulness of buccal Ring, Adair and Elwyn (RAE) oxygenation has been established in previous studies, however a head-to-head comparison with nasal cannula (NC) is lacking.Aim:The aim of this study was to compare apnoea time with buccal RAE (BR) versus NC in obese patients.Setting and Design:This was a prospective, nonblinded randomized controlled trial conducted in a tertiary hospital where fifty American Society of Anaesthesiologists Physical Status Class I and II, obese patients with body mass index ≥30, posted for elective surgery were included.Materials and Methods:Following adequate preoxygenation and standard induction of anaesthesia, a prolonged simulated difficult laryngoscopy was performed during which oxygen was provided via either BR or NC. The primary outcome was time to desaturation to <95% or 10 min, which ever occurred first. Other outcomes recorded were lowest saturation, time to resaturation and highest end tidal carbon di oxide.Statistical Analysis:Mean with standard deviation (SD) or median with inter quartile range were used for continuous variables and absolute number with percentage were used for categorical variables. The primary outcome was analyzed using Kaplan-Meier survival curves, and log-rank tests were applied.Results:Patient characteristics were similar in both arms. The mean apnoea time in seconds (SD) in the BR group, 375.3 (116.6) was higher than the NC group 316.1 (94.1), P = 0.054. From the Kapan Meier curves the probability of desaturating to <95% was earlier in the NC group than the BR group (P = 0.092). The other outcomes were similar in both groups.Conclusion:This is the first study that demonstrates that oxygenation via a BR is better than NC in providing apnoeic oxygenation in obese patients and can safely be used when NC are contraindicated.

Structure and Thermodynamics of Eu(III) and Cm(III) Complexes with Glucuronic Acid.

Complexation by small organic ligands controls the bioavailability of contaminants and influences their mobility in the geosphere. We have studied the interactions of Cm3+, as a representative of the trivalent actinides, and Eu3+, as an inactive homologue, with glucuronic acid (GlcA) a simple sugar acid. Time-resolved laser-induced luminescence spectroscopy (TRLFS) shows that complexation at pH 5.0 occurs only at high ligand to metal ratios in the form of 1:1 complexes with standard formation constants log β0 = 1.84 ± 0.22 for Eu3+ and log β0 = 2.39 ± 0.19 for Cm3+. A combination of NMR, QMMM, and TRLFS reveals the structure of the complex to be a half-sandwich structure wherein the ligand binds through its carboxylic group, the ring oxygen, and a hydroxyl group in addition to five to six water molecules. Surprisingly, Y3+, which was used as a diamagnetic reference in NMR, prefers a different coordination geometry with bonding through at least two hydroxyl groups on the opposite side of a distorted GlcA molecule. QMMM simulations indicate that the differences in stability among Cm, Eu, and Y are related to ring strain induced by smaller cations. At higher pH a stronger complex was detected, most likely due to deprotonation of a coordinating OH group.

Physiological responses of Douglas-fir to climate and forest disturbances as detected by cellulosic carbon and oxygen isotope ratios.

Swiss needle cast (SNC), caused by a fungal pathogen, Nothophaeocryptopus gaeumannii, is a major forest disease of Douglas-fir (Pseudotsuga menziesii) stands of the Pacific Northwest (PNW). There is mounting concern that the current SNC epidemic occurring in Oregon and Washington will continue to increase in severity, frequency and spatial extent with future warming. Nothophaeocryptopus gaeumannii occurs wherever its host is found, but very little is known about the history and spatial distribution of SNC and its effects on growth and physiological processes of mature and old-growth forests within the Douglas-fir region of the PNW. Our findings show that stem growth and physiological responses of infected Douglas-fir to climate and SNC were different between sites, growth periods and disease severity based on cellulosic stable carbon and oxygen isotope ratios and ring width data in tree rings. At a coastal Oregon site within the SNC impact zone, variations in stem growth and Δ13C were primarily influenced by disproportional reductions in stomatal conductance (gs) and assimilation (A) caused by a loss of functioning stomates through early needle abscission and stomatal occlusion by pseudothecia of N. gaeumannii. At the less severely infected inland sites on the west slopes of Oregon's Cascade Range, stem growth correlated negatively with δ18O and positively with Δ13C, indicating that gs decreased in response to high evaporative demand with a concomitant reduction in A. Current- and previous-years summer vapor pressure deficit was the principal seasonal climatic variable affecting radial stem growth and the dual stable isotope ratios at all sites. Our results indicate that rising temperatures since the mid-1970s has strongly affected Douglas-fir growth in the PNW directly by a physiological response to higher evaporative demand during the annual summer drought and indirectly by a major SNC epidemic that is expanding regionally to higher latitudes and higher elevations.

Roseophilin-inspired derivatives as transmembrane anion carriers

ABSTRACT Roseophilin is an alkaloid structurally related to prodiginines . The intriguing pharmacological properties of these derivatives have prompted us to prepare synthetic compounds 1–3 inspired by their structure and to explore their transmembrane anion transport activity. The methoxyfuran heterocycle impacts the anionophoric activity of the compounds as a result of the reduced hydrogen-bonding ability and electrostatic repulsions between the oxygen in the furan ring and the anions. The position of the furan was also found to be crucial for determining their anion transport activity. Overall, replacement of the characteristic methoxypyrrole moiety of prodiginines and tambjamines by the methoxyfuran found in roseophilin is detrimental to their ability as anion carriers, suggesting that the biological activity of roseophilin is likely not related to their potential activity as anion carriers. Compound 2, bearing a furan ring attached to a dipyrromethene moiety, was found to be the most active anion carrier.

Comparative genomic analysis of azasugar biosynthesis

Azasugars are monosaccharide analogs in which the ring oxygen is replaced with a nitrogen atom. These well-known glycosidase inhibitors are of interest as therapeutics, yet several aspects of azasugars remain unknown including their distribution, structural diversity, and chemical ecology. The hallmark signature of bacterial azasugar biosynthesis is a three gene cluster (3GC) coding for aminotransferase, phosphatase, and dehydrogenase enzymes. Using the bioinformatics platform Enzyme Similarity Tool (EST), we identified hundreds of putative three gene clusters coding for azasugar production in microbial species. In the course of this work, we also report a consensus sequence for the aminotransferase involved in azasugar biosynthesis as being: SGNXFRXXXFPNXXXXXXXLXVPXPYCXRC. Most clusters are found in Bacillus and Streptomyces species which typically inhabit soil and the rhizosphere, but some clusters are found with diverse species representation such as Photorhabdus and Xenorhabdus which are symbiotic with entomopathogenic nematodes; the human skin commensal Cutibacterium acnes, and the marine Bacillus rugosus SPB7, a symbiont to the sea sponge Spongia officinalis. This pan-taxonomic survey of the azasugar 3GC signature may lead to the identification of new azasugar producers, facilitate studies of their natural functions, and lead to new potential therapeutics.

Effects of azole rings with different chalcogen atoms on ESIPT behavior for benzochalcogenazolyl-substituted hydroxyfluorenes

ESIPT behavior has attracted a lot of eyes of researchers in recent years because of its unique optical properties. Due to its large Stokes shift and double emission fluorescence, white light can be generated in the fluorophore based on the excited state intramolecular proton transfer (ESIPT) principle. The excited state proton transfer behavior of hydroxylated benzoxazole (BO-OH), benzothiazole (BS-OH) and benzoselenazole (BSe-OH) have been investigated in heptane, chloroform and DMF solvents. By comparing the infrared vibration spectra and the variation of bond parameters from the S0 to S1 states, and analyzing the frontier molecular orbitals, the influence of hydrogen bond dynamics, the solvent polarity, charge redistribution and the effects of different proton acceptors on proton transfer were observed. The only structural difference among the three substituted hydroxyfluorenes is the heteroatom in the azole ring (oxygen, sulfur and selenium, respectively). We have scanned the potential energy curve of the ESIPT process, and compared the potential barrier, it is found that the heavier chalcogen atoms are more favorable for proton transfer. At the same time, the potential application of changing heteroatoms in the azole ring by walking down the chalcogenic group in crystal luminescence color regulation is also discussed.

In-situ UV cured acrylonitrile grafted epoxidized natural rubber (ACN-g-ENR) – LiTFSI solid polymer electrolytes for lithium-ion rechargeable batteries

Solid polymer electrolytes (SPEs) of newly synthesized acrylonitrile grafted epoxidized natural rubber (ACN-g-ENR) were successfully prepared with lithium bis(trifluoromethanesulfonyl)imide salt (LiTFSI) via UV curing technique. The highest ionic conductivity of the SPEs was accomplished at 40 wt% LiTFSI with conductivity value of 1.1 × 10−6 S cm−1 at room temperature. Further analysis indicates that the ion transport of the SPEs follows the VTF model. Chronoamperometry study estimated low lithium ions contribution to overall ionic conductivity (ca. 3%). A persuasive value of 2.7 V was obtained from the electrochemical stability. It is suitable to be applied in lithium-ion rechargeable batteries. An additional investigation by infrared (FTIR) spectroscopy revealed the polymer salt complexation occurred between Li+ of dopant salt with the ether group (C-O-C) oxygen of the epoxy ring. The inclusion of LiTFSI salts was decreased crystallinity, nevertheless, the glass transition temperature (Tg) and thermal stability, as well as the dynamic mechanical properties of the polymer electrolytes were enhanced. All in all, the initial electrochemical characteristics showed a promising potential of ACN-g-ENR host polymeric electrolyte to be used in lithium-ion storage energy applications.

Tridentate imidazole-based Schiff base metal complexes: molecular docking, structural and biological studies

A novel Schiff base was synthesized by the condensation of imidazole-2-carboxaldehyde with l-histidine in an equimolar ratio. The prepared Schiff base was characterized by elemental analysis and spectral characterization techniques. It was then complexed with a series of 3-d metal(II) ions like manganese, iron, cobalt, nickel, copper and zinc. The coordination properties, nature of bonding and stability of the complexes were deduced from elemental analysis, IR, UV–vis, 1H NMR, mass, electronic spectra, magnetic, conductivity and thermogravimetric analysis. IR studies support the tridentate behaviour of Schiff base as well as its coordination to the central metal ion through an azomethine nitrogen, deprotonated carboxylic oxygen and imidazole ring nitrogen atoms of histidine. The electronic spectra and magnetic moment data demonstrate that the complexes have an octahedral geometry, except zinc complex, which has a tetrahedral geometry. In vitro antimicrobial activity of the synthesized compounds has been shown to exhibit excellent antibacterial and antifungal activities. The antibacterial property of the prepared Schiff base was further confirmed by conducting a docking study of target proteins involved in the antibacterial mechanism. Communicated by Ramaswamy H. Sarma

Biosynthesis of the Tricyclic Aromatic Type II Polyketide Rishirilide: New Potential Third Ring Oxygenation after Three Cyclization Steps

Rishirilides are a group of PKS II secondary metabolites produced by Streptomyces bottropensis Gö C4/4. Biosynthetic studies in the past have elucidated early and late steps of rishirilide biosynthesis. This work is aiming to solve the remaining steps in the rishirilide biosynthesis. Inactivation of the cyclase gene rslC3 in Streptomyces bottropensis resulted in an interruption of rishirilide production. Instead, accumulation of the tricyclic aromatic galvaquinones was observed. Similar results were observed after deletion of rslO4. Closer inspection into RslO4 crystal structure in addition to site-directed mutagenesis and molecular dynamic simulations revealed that RslO4 might be responsible for quinone formation on the third ring. The RslO1 three-dimensional structure shows a high similarity to FMN-dependent luciferase-like monooxygenases such as the epoxy-forming MsnO8 which acts with the flavin reductase MsnO3 in mensacarcin biosynthesis in the same strain. The high sequence similarity between RslO2 and MsnO3 suggests that RslO2 provides RslO1 with reduced FMN to form an epoxide that serves as substrate for RslO5.

Conductance selectivity of Na+ across the K+ channel via Na+ trapped in a tortuous trajectory

Ion selectivity of the potassium channel is crucial for regulating electrical activity in living cells; however, the mechanism underlying the potassium channel selectivity that favors large K+ over small Na+ remains unclear. Generally, Na+ is not completely excluded from permeation through potassium channels. Herein, the distinct nature of Na+ conduction through the prototypical KcsA potassium channel was examined. Single-channel current recordings revealed that, at a high Na+ concentration (200 mM), the channel was blocked by Na+, and this blocking was relieved at high membrane potentials, suggesting the passage of Na+ across the channel. At a 2,000 mM Na+ concentration, single-channel Na+ conductance was measured as one-eightieth of the K+ conductance, indicating that the selectivity filter allows substantial conduit of Na+ Molecular dynamics simulations revealed unprecedented atomic trajectories of Na+ permeation. In the selectivity filter having a series of carbonyl oxygen rings, a smaller Na+ was distributed off-center in eight carbonyl oxygen-coordinated sites as well as on-center in four carbonyl oxygen-coordinated sites. This amphipathic nature of Na+ coordination yielded a continuous but tortuous path along the filter. Trapping of Na+ in many deep free energy wells in the filter caused slow elution. Conversely, K+ is conducted via a straight path, and as the number of occupied K+ ions increased to three, the concerted conduction was accelerated dramatically, generating the conductance selectivity ratio of up to 80. The selectivity filter allows accommodation of different ion species, but the ion coordination and interactions between ions render contrast conduction rates, constituting the potassium channel conductance selectivity.

Visible-Light Responsive Sucrose-Containing Macrocyclic Host for Cations.

Chiral photoresponsive host 1 was prepared by a high-yield Cs2CO3-templated macrocyclization. Trans-1 transforms into long-lived cis-1 (25 days) upon irradiation with green light, and the backward transformation is triggered by blue light. Both isomers prefer potassium among alkali metal cations, and cis-1 binds cations stronger than trans-1 (Kcis/Ktrans ≤ 4.1). 1H NMR titration experiments as well as density functional theory studies reveal that sucrose ring oxygen residues and azobenzene nitrogen atoms in 1 contribute to cation coordination.

FRET-based ‘ratiometric’ molecular switch for multiple ions with efficacy towards real-time sampling and logic gate applications

Fluorescent nanoaggregates comprised of rhodamine based amphiphilic probe has been designed, which can simultaneously detect Al 3+ , Cr 3+ and F¯ ions in the aqueous medium (pH 7.4). Mechanistic investigation indicates that both the carbonyl oxygen of the spirolactam ring and the nitrogen center of indole participate in the coordination of metal ions. Consequently, metal ion-binding induces the opening of the spirolactam ring and allows the Förster energy transfer from indole to xanthene moiety. As a result, the colorless probe solution turns pink in presence of metal ions, with ratiometric fluorescence change from blue to yellow. Further, the addition of fluoride leads to dissociation of preformed Al 3+ -complex, resulting in the fading of pink color and reverting the fluorescence signal to the original. This not only serves as a tool to discriminate between Al 3+ and Cr 3+ ion but also acts as a strategy for detecting fluoride in the aqueous medium. Thus, using a single FRET probe, ‘ratiometric’, naked-eye sensing of multiple ions was achieved. Also, considering the differential response of probe molecule towards Cr(III) and Cr(VI), a colorimetric assay for biogenic thiols was developed. Simultaneously, a combinatorial molecular logic gate was designed based on the multiple ion sensing ability of the probe molecule. Further, the system showed real-time detection of Al 3+ and Cr 3+ in natural water samples, estimation of Al 3+ in antacid tablets and fluoride in mouthwash, etc. Lastly, low-cost, reusable paper strips were developed, which offers an alternative strategy for on-site detection of metal ions without engaging any sophisticated instruments or trained personnel. • Ratiometric sensing of Al 3+ , Cr 3+ and F − ions at nanomolar levels in water. • Assay for biogenic thiols based on differential response for Cr(III) and Cr(VI). • Design combinatorial logic gate based on multiple ion sensing. • Analysis of real-life samples: fluoride in mouthwash, Aluminium in antacid tablets. • Low-cost, reusable paper strips for onsite detection of ions.

On the Origin of Regioselectivity in Palladium‐Catalyzed Oxidation of Glucosides

AbstractThe palladium‐catalyzed oxidation of glucopyranosides has been investigated using relativistic density functional theory (DFT) at ZORA‐BLYP−D3(BJ)/TZ2P. The complete Gibbs free energy profiles for the oxidation of secondary hydroxy groups at C2, C3, and C4 were computed for methyl β‐glucoside and methyl carba‐β‐glucoside. Both computations and oxidation experiments on carba‐glucosides demonstrate the crucial role of the ring oxygen in the C3 regioselectivity observed during the oxidation of glucosides. Analysis of the model systems for oxidized methyl β‐glucoside shows that the C3 oxidation product is intrinsically favored in the presence of the ring oxygen. Subsequent energy decomposition analysis (EDA) and Hirschfeld charge analysis reveal the role of the ring oxygen: it positively polarizes C1/C5 by inductive effects and disfavors any subsequent buildup of positive charge at neighboring carbon atoms, rendering C3 the most favored site for the β‐hydride elimination.

Oxygen Isotopes in Tree Rings from Greenland: A New Proxy of NAO

We present the first Greenlandic tree ring oxygen isotope record (δ18OGTR), derived from four birch trees collected from the Qinguadalen Valley in southwestern Greenland in 1999. Our δ18O record spans from 1950–1999 and is significantly and positively correlated with winter ice core δ18O from southern Greenland. δ18OGTR records are positively correlated with southwestern Greenland January–August mean temperatures. North Atlantic Oscillation (NAO) reconstructions have been developed from a variety of proxies, but never with Greenlandic tree rings, and our δ18OGTR record is significantly correlated with NAO (r = −0.64), and spatial correlations with sea-level pressure indicate a classic NAO pressure seesaw pattern. These results may facilitate a longer NAO reconstruction based on long time series of tree ring δ18O records from Greenland, provided that subfossil wood can be found in areas vacated by melting glaciers.