A transient peak in marine sulfate after the 635-Ma snowball Earth.

SignificanceEarth system's response to major perturbations is of paramount interest. On the basis of multiple isotope compositions for pyrite, carbonate-associated sulfate, carbonates, and organics within, we inferred that the much-debated, enigmatic, extremely 13C-depleted calcite cements in the ∼635-Ma cap carbonates in South China preserve geochemical evidence for marine microbial sulfate reduction coupled to anaerobic oxidation of methane. This interpretation implies the existence of a brief interval of modern-level marine sulfate. We determined that this interval coincides with the earliest Ediacaran 17O-depletion episode, and both likely occurred within ∼50 ky since the onset of the 635-Ma meltdown, revealing an astonishing pace of transformation of the Earth system in the aftermath of Earth's latest snowball glaciation.

Quantitative 17 O MRSI of myocardial oxygen metabolic rate, blood flow, and oxygen extraction fraction under normal and high workload conditions.

PURPOSE: The heart is a highly aerobic organ consuming most of the oxygen the body in supporting heart function. Quantitative imaging of myocardial oxygen metabolism and perfusion is essential for studying cardiac physiopathology in vivo. Here, we report a new imaging method that can simultaneously assess myocardial oxygen metabolism and blood flow in the rat heart. METHODS: This novel method is based on the 17 O-MRSI combined with brief inhalation of 17 O-isotope labeled oxygen gas for quantitative imaging of myocardial metabolic rate of oxygen consumption (MVO2 ), myocardial blood flow (MBF), and oxygen extraction fraction (OEF). We demonstrate this imaging method under basal and high workload conditions in rat hearts at 9.4 T. RESULTS: We show that this 17 O MRSI-based approach can directly measure and image MVO2 (1.35-4.06 µmol/g/min), MBF (0.49-1.38 mL/g/min), and OEF (0.33-0.44) in the heart of anesthetized rat under basal and high workload (21.6 × 103 -56.7 × 103 mmHg • bpm) conditions. Under high workload condition, MVO2 and MBF values in healthy rats approximately doubled, whereas OEF remained unchanged, indicating a strong coupling between myocardial oxygen metabolic demand and supply through blood perfusion. CONCLUSION: The 17 O-MRSI method has been used to simultaneously image the myocardial metabolic rate of oxygen consumption, blood flow, and oxygen extraction fraction in small animal hearts, which are sensitive to the physiological changes induced by high workload. This approach could provide comprehensive measures that are critical for studying myocardial function in normal and diseased states and has a potential for translation.

Probing oxygen exchange between UiO-66(Zr) MOF and water using 17 O solid-state NMR.

The Zr-based Metal Organic Framework (MOF) UiO-66(Zr) is widely employed owing to its good thermal and chemical stabilities. Although the long-range structure of this MOF is preserved in the presence of water during several days, little is known about the formation of defects, which cannot be detected using diffraction techniques. We apply here 17 O solid-state NMR spectroscopy at 18.8 T to investigate the reactivity of UiO-66, through the exchange of oxygen atoms between the different sites of the MOF and water. For that purpose, we have selectively enriched in 17 O isotope the carboxylate groups of UiO-66(Zr) by using it with 17 O-labeled terephthalic acid prepared using mechanochemistry. In the presence of water at 50 °C and a following dehydration at 150 °C, we observe an overall exchange of O atoms between COO- and µ3 -O2- sites. Furthermore, we demonstrate that the three distinct oxygen sites, µ3 -OH, µ3 -O2- and COO- , of UiO-66(Zr) MOF can be enriched in 17 O isotope by post-synthetic hydrothermal treatment in the presence of 17 O-enriched water. These results demonstrate the lability of Zr-O bonds and the reactivity of UiO-66(Zr) with water.

Isotope Effects and the Atmosphere.

Chemical physics plays a large role in determining the isotopic compositions of gases in Earth's atmosphere, which in turn provide fundamental insights into the sources, sinks, and transformations of atmospheric gases and particulates and their influence on climate. This review focuses on the kinetic and photolysis isotope effects relevant to understanding the isotope compositions of atmospheric ozone, carbon dioxide, methane, nitrous oxide, and other gases and their historical context. The discussion includes non-mass-dependent isotope compositions of oxygen-containing species and a brief overview of the recent growth of clumped isotope measurements at natural isotopic abundances, that is, of molecules containing more than one rare isotope. The intention is to introduce chemistry researchers to the field of using isotope compositions as tracers of atmospheric chemistry and climate both today and back in time through ice and rock records and to highlight the outstanding research questions to which experimental and theoretical physical chemists can contribute.

Fast and Cost-Efficient 17 O-Isotopic Labeling of Carboxylic Groups in Biomolecules: From Free Amino Acids to Peptide Chains.

17 O NMR spectroscopy is a powerful technique, which can provide unique information regarding the structure and reactivity of biomolecules. However, the low natural abundance of 17 O (0.04 %) generally requires working with enriched samples, which are not easily accessible. Here, we present simple, fast and cost-efficient 17 O-enrichment strategies for amino acids and peptides by using mechanochemistry. First, five unprotected amino acids were enriched under ambient conditions, consuming only microliter amounts of costly labeled water, and producing pure molecules with enrichment levels up to ∼40 %, yields ∼60-85 %, and no loss of optical purity. Subsequently, 17 O-enriched Fmoc/tBu-protected amino acids were produced on a 1 g/day scale with high enrichment levels. Lastly, a site-selective 17 O-labeling of carboxylic functions in peptide side-chains was achieved for RGD and GRGDS peptides, with ∼28 % enrichment level. For all molecules, 17 O ssNMR spectra were recorded at 14.1 T in reasonable times, making this an important step forward for future NMR studies of biomolecules.

First Measurements on Triple Oxygen Isotopes of Dissolved Inorganic Phosphate in the Hydrosphere.

Although dissolved inorganic phosphate (DIP) is an important nutrient in the hydrosphere, it is difficult to quantitatively clarify the dynamics of DIP in the hydrosphere using the δ18O value of DIP as a tracer. In this study, we quantified the triple oxygen isotopic compositions (Δ'17O) of DIP relative to VSMOW with the reference line with a slope of 0.528 as an additional tracer to clarify the sources and dynamics of DIP in the hydrosphere. We found significant variation in the Δ'17O values of riverine DIP in urban areas, ranging from -107 × 10-6 to +3 × 10-6, while those of DIP in the effluents from wastewater treatment plants (WWTP) and DIP extracted from the chemical fertilizers showed -56 ± 5 × 10-6 (1SD) and -98 ± 5 × 10-6, respectively. We conclude that both the DIP supplied directly from the artificial loads (the WWTP effluent and chemical fertilizers) showing 17O-depleted Δ'17O values and the DIP turned over via the aquatic biosphere showing 17O-enriched Δ'17O values similar to ambient H2O were the major sources of riverine DIP. High-precision determination of the Δ'17O value of DIP can contribute to quantitative clarification of the dynamics of DIP in the hydrosphere.

Dominant Contribution of NO3 Radical to NO3- Formation during Heavy Haze Episodes: Insights from High-Time Resolution of Dual Isotopes Δ17O and δ18O.

δ18O is widely used to track nitrate (NO3-) formation but overlooks NO3 radical reactions with hydrocarbons (HCs), particularly in heavily emitting hazes. This study introduces high-time resolution Δ17O-NO3- as a powerful tool to quantify NO3- formation during five hazes in three cities. Results show significant differences between Δ17O-NO3- and δ18O-NO3- in identifying NO3- formation. δ18O-NO3- results suggested N2O5 hydrolysis (62.0-88.4%) as the major pathway of NO3- formation, while Δ17O-NO3- shows the NO3- formation contributions of NO2 + OH (17.7-66.3%), NO3 + HC (10.8-49.6%), and N2O5 hydrolysis (22.9-33.3%), revealing significant NO3 + HC contribution (41.7-56%) under severe pollution. Furthermore, NO3- formation varies with temperatures, NOx oxidation rate (NOR), and pollution levels. Higher NO2 + OH contribution and lower NO3 + HC contribution were observed at higher temperatures, except for low NOR haze where higher NO2 + OH contributions were observed at low temperatures (T ← 10 °C). This emphasizes the significance of NO2 + OH in emission-dominated haze. Contributions of NO2 + OH and NO3 + HC relate to NOR as positive (fP1 = 3.0*NOR2 - 2.4*NOR + 0.8) and negative (fP2 = -2.3*NOR2 + 1.8*NOR) quadratic functions, respectively, with min/max values at NOR = 0.4. At mild pollution, NO2 + OH (58.1 ± 22.2%) dominated NO3- formation, shifting to NO3 + HC (35.5 ± 16.3%) during severe pollution. Additionally, high-time resolution Δ17O-NO3- reveals that morning-evening rush hours and high temperatures at noon promote the contributions of NO3 + HC and NO2 + OH, respectively. Our results suggested that the differences in the NO3- pathway are attributed to temperatures, NOR, and pollution levels. Furthermore, high-time resolution Δ17O-NO3- is vital for quantifying NO3 + HC contribution during severe hazes.

Functional stability of water wire-carbonyl interactions in an ion channel.

Water wires are critical for the functioning of many membrane proteins, as in channels that conduct water, protons, and other ions. Here, in liquid crystalline lipid bilayers under symmetric environmental conditions, the selective hydrogen bonding interactions between eight waters comprising a water wire and a subset of 26 carbonyl oxygens lining the antiparallel dimeric gramicidin A channel are characterized by 17O NMR spectroscopy at 35.2 T (or 1,500 MHz for 1H) and computational studies. While backbone 15N spectra clearly indicate structural symmetry between the two subunits, single site 17O labels of the pore-lining carbonyls report two resonances, implying a break in dimer symmetry caused by the selective interactions with the water wire. The 17O shifts document selective water hydrogen bonding with carbonyl oxygens that are stable on the millisecond timescale. Such interactions are supported by density functional theory calculations on snapshots taken from molecular dynamics simulations. Water hydrogen bonding in the pore is restricted to just three simultaneous interactions, unlike bulk water environs. The stability of the water wire orientation and its electric dipole leads to opposite charge-dipole interactions for K+ ions bound at the two ends of the pore, thereby providing a simple explanation for an ∼20-fold difference in K+ affinity between two binding sites that are ∼24 Šapart. The 17O NMR spectroscopy reported here represents a breakthrough in high field NMR technology that will have applications throughout molecular biophysics, because of the acute sensitivity of the 17O nucleus to its chemical environment.

Triple oxygen isotope insight into terrestrial pyrite oxidation.

The mass-independent minor oxygen isotope compositions (Δ'17O) of atmospheric O2 and [Formula: see text] are primarily regulated by their relative partial pressures, [Formula: see text]/[Formula: see text] Pyrite oxidation during chemical weathering on land consumes [Formula: see text] and generates sulfate that is carried to the ocean by rivers. The Δ'17O values of marine sulfate deposits have thus been proposed to quantitatively track ancient atmospheric conditions. This proxy assumes direct [Formula: see text] incorporation into terrestrial pyrite oxidation-derived sulfate, but a mechanistic understanding of pyrite oxidation-including oxygen sources-in weathering environments remains elusive. To address this issue, we present sulfate source estimates and Δ'17O measurements from modern rivers transecting the Annapurna Himalaya, Nepal. Sulfate in high-elevation headwaters is quantitatively sourced by pyrite oxidation, but resulting Δ'17O values imply no direct tropospheric [Formula: see text] incorporation. Rather, our results necessitate incorporation of oxygen atoms from alternative, 17O-enriched sources such as reactive oxygen species. Sulfate Δ'17O decreases significantly when moving into warm, low-elevation tributaries draining the same bedrock lithology. We interpret this to reflect overprinting of the pyrite oxidation-derived Δ'17O anomaly by microbial sulfate reduction and reoxidation, consistent with previously described major sulfur and oxygen isotope relationships. The geologic application of sulfate Δ'17O as a proxy for past [Formula: see text]/[Formula: see text] should consider both 1) alternative oxygen sources during pyrite oxidation and 2) secondary overprinting by microbial recycling.

17 O nuclear magnetic resonance: Recent advances and applications.

The present review is focused on the most recent achievements in the application of liquid phase 17 O nuclear magnetic resonance (NMR) to inorganic, organic, and biochemical molecules focusing on their structure, conformations, and (bio)chemical behavior. The review is composed of four basic parts, namely, (1) simple molecules; (2) water and hydrogen bonding; (3) metal oxides, clusters, and complexes; and (4) biological molecules. Experimental 17 O NMR chemical shifts are thoroughly tabulated. They span a range of as much as almost 650 ppm (from -35.6 to +610.0 ppm) for inorganic and organic molecules, whereas this range is much wider for biological species being of about 1350 ppm (from -12 to +1332 ppm), and in the case of hemoproteins and heme-model compounds, isotropic chemical shifts of up to 2500 ppm were observed. The general prospects and caveats in the modern development of the liquid phase 17 O NMR in chemistry and biochemistry are critically discussed and briefly outlined in view of their future applications.

17 O Hyperfine Spectroscopy Reveals Hydration Structure of Nitroxide Radicals in Aqueous Solutions.

The hydration structure of nitroxide radicals in aqueous solutions is elucidated by advanced 17 O hyperfine (hf) spectroscopy with support of quantum chemical calculations and MD simulations. A piperidine and a pyrrolidine-based nitroxide radical are compared and show clear differences in the preferred directionality of H-bond formation. We demonstrate that these scenarios are best represented in 17 O hf spectra, where in-plane coordination over σ ${\sigma }$ -type H-bonding leads to little spin density transfer on the water oxygen and small hf couplings, whereas π ${{\rm \pi }}$ -type perpendicular coordination generates much larger hf couplings. Quantitative analysis of the spectra based on MD simulations and DFT predicted hf parameters is consistent with a distribution of close solvating water molecules, in which directionality is influenced by subtle steric effects of the ring and the methyl group substituents.

Phase I Randomized Trial of 17 O-Labeled Water: Safety and Feasibility Study of Indirect Proton MRI for the Evaluation of Cerebral Water Dynamics.

BACKGROUND: 17 O-labeled water (PSO17) is a contrast agent developed to measure brain water dynamics and cerebral blood flow. PURPOSE: To evaluate the safety and feasibility of PSO17. STUDY TYPE: Prospective study. SUBJECTS: A total of 12 male healthy volunteers (23.1 ± 1.9 years) were assigned to three groups of four subjects: placebo (normal saline), PSO17 10%, and PSO17 20%. FIELD STRENGTH/SEQUENCE: Dynamic 3D fluid attenuated inversion recovery (FLAIR, fast spin echo with variable refocusing flip angle) scans of the brain were performed with 3-T MRI. ASSESSMENT: Contrast agents were injected 5 minutes after the start of a 10-minute scan. Any symptoms, vital signs, and blood and urine tests were evaluated at five timepoints from preinjection to 4 days after. Blood samples for pharmacokinetic analysis, including half-life (T1/2), maximum fraction (Cmax ), time-to-maximum fraction (Tmax ), and area under the curve (AUC), were collected at 13 timepoints from preinjection to 168 hours after. Regions of interest were set in the cerebral cortex (CC), basal ganglia/thalamus (BG/TM), and white matter (WM), and 17 O concentrations were calculated from signal changes and evaluated using Cmax . STATISTICAL TESTS: All items were compared among the three groups using Tukey-Kramer's honestly significant difference test. Statistical significance was defined as P < 0.5. RESULTS: No safety issues were noted with the intravenous administration of PSO17. The T1/2 was approximately 160 hours, and the AUCs were 1.77 ± 0.10 and 3.75 ± 0.36 in the PSO17 10% and 20% groups, respectively. 17 O fractions calculated from MRI signals were higher in the PSO17 20% group than in the 10% and placebo groups. Significant differences were noted between all pairs of groups in the CC and BG/TM, and between PSO17 20% and both placebo and 10% groups in the WM. DATA CONCLUSION: PSO17 might be considered safe as a contrast medium. Dynamic 3D-FLAIR might detect dose-dependent signal changes and estimate 17 O. EVIDENCE LEVEL: 1 TECHNICAL EFFICACY: Stage 1.

EPR Evidence for Mechanistic Diversity of Cu(II)/Peroxygen Oxidation Systems by Tracing the Origin of DMPO Spin Adducts.

Electron paramagnetic resonance (EPR) has been extensively used for the identification of free radicals that are generated from advanced oxidation processes (AOPs) so as to establish the reaction mechanism. However, some misinterpretations or controversies on the identity of detected EPR signals remain in the literature. This study, with Cu(II)-based AOPs as examples, comprehensively investigated the origin of 5,5-dimethyl-l-pyrroline N-oxide (DMPO) adducts in Cu(II) alone, Cu(II)/H2O2, Cu(II)/peroxymonosulfate (PMS), and Cu(II)/peroxydisulfate (PDS) systems. In most Cu(II) systems, DMPO-OH signals can be detected even without any peroxygens, indicating the presence of other origins of this adduct in addition to the genuine spin trapping of •OH by DMPO. According to the formed secondary radical adducts (DMPO-OCH3 from a nonradical process or DMPO-CH2OH from a radical oxidation) derived from methanol quenching, we propose that CuO+, instead of free radicals, is involved in the Cu(II)/PMS system, while •OH is indeed generated in the Cu(II)/H2O2 and Cu(II)/PDS systems under neutral conditions. Notably, 17O-incorporation experiments demonstrate that -OH in the detected DMPO-OH adduct originates 100% from water in the Cu(II) alone system but the amount of -OH is over 99.8% from the oxidant while peroxygens are added. In addition, DMPO-O2- appears only in the Cu(II)/PDS system under highly alkaline conditions and H2O is not involved in superoxide formation.

17 O NMR Studies of Yeast Ubiquitin in Aqueous Solution and in the Solid State.

We report a general method for amino acid-type specific 17 O-labeling of recombinant proteins in Escherichia coli. In particular, we have prepared several [1-13 C,17 O]-labeled yeast ubiquitin (Ub) samples including Ub-[1-13 C,17 O]Gly, Ub-[1-13 C,17 O]Tyr, and Ub-[1-13 C,17 O]Phe using the auxotrophic E. coli strain DL39 GlyA λDE3 (aspC- tyrB- ilvE- glyA- λDE3). We have also produced Ub-[η-17 O]Tyr, in which the phenolic group of Tyr59 is 17 O-labeled. We show for the first time that 17 O NMR signals from protein terminal residues and side chains can be readily detected in aqueous solution. We also reported solid-state 17 O NMR spectra for Ub-[1-13 C,17 O]Tyr and Ub-[1-13 C,17 O]Phe obtained at an ultrahigh magnetic field, 35.2 T (1.5 GHz for 1 H). This work represents a significant advance in the field of 17 O NMR studies of proteins.

Quantitative and simultaneous measurement of oxygen consumption rates in rat brain and skeletal muscle using 17 O MRS imaging at 16.4T.

PURPOSE: Oxygen-17 (17 O) MRS imaging, successfully used in the brain, is extended by imaging the oxygen metabolic rate in the resting skeletal muscle and used to determine the total whole-body oxygen metabolic rate in the rat. METHODS: During and after inhalations of 17 O2 gas, dynamic 17 O MRSI was performed in rats (n = 8) ventilated with N2 O or N2 at 16.4 T. Time courses of the H217 O concentration from regions of interest located in brain and muscle tissue were examined and used to fit an animal-adapted 3-phase metabolic model of oxygen consumption. CBF was determined with an independent washout method. Finally, body oxygen metabolic rate was calculated using a global steady-state approach. RESULTS: Cerebral metabolic rate of oxygen consumption was 1.97 ± 0.19 µmol/g/min on average. The resting metabolic rate of oxygen consumption in skeletal muscle was 0.32 ± 0.12 µmol/g/min and >6 times lower than cerebral metabolic rate of oxygen consumption. Global oxygen consumed by the body was 24.2 ± 3.6 mL O2 /kg body weight/min. CBF was estimated to be 0.28 ± 0.02 mL/g/min and 0.34 ± 0.06 mL/g/min for the N2 and N2 O ventilation condition, respectively. CONCLUSION: We have evaluated the feasibility of 17 O MRSI for imaging and quantifying the oxygen consumption rate in low metabolizing organs such as the skeletal muscle at rest. Additionally, we have shown that CBF is slightly increased in the case of ventilation with N2 O. We expect this study to be beneficial to the application of 17 O MRSI to a wider range of organs, although further validation is advised.

Labeling and Probing the Silica Surface Using Mechanochemistry and 17 O†NMR Spectroscopy*.

In recent years, there has been increasing interest in developing cost-efficient, fast, and user-friendly 17 O enrichment protocols to help to understand the structure and reactivity of materials by using 17 O NMR spectroscopy. Here, we show for the first time how ball milling (BM) can be used to selectively and efficiently enrich the surface of fumed silica, which is widely used at industrial scale. Short milling times (up to 15 min) allowed modulation of the enrichment level (up to ca. 5 %) without significantly changing the nature of the material. High-precision 17 O compositions were measured at different milling times by using large-geometry secondary-ion mass spectrometry (LG-SIMS). High-resolution 17 O NMR analyses (including at 35.2 T) allowed clear identification of the signals from siloxane (Si-O-Si) and silanols (Si-OH), while DNP analyses, performed by using direct 17 O polarization and indirect 17 O{1 H} CP excitation, agreed with selective labeling of the surface. Information on the distribution of Si-OH environments at the surface was obtained from 2D 1 H-17 O D-HMQC correlations. Finally, the surface-labeled silica was reacted with titania and using 17 O DNP, their common interface was probed and Si-O-Ti bonds identified.

Indirectly Detected DNP-Enhanced 17 O NMR Spectroscopy: Observation of Non-Protonated Near-Surface Oxygen at Naturally Abundant Silica and Silica-Alumina.

Recent studies have shown that dynamic nuclear polarization (DNP) can be used to detect 17 O solid-state NMR spectra of naturally abundant samples within a reasonable experimental time. Observations using indirect DNP, which relies on 1 H mediation in transferring electron hyperpolarization to 17 O, are currently limited mostly to hydroxyls. Direct DNP schemes can hyperpolarize non-protonated oxygen near the radicals; however, they generally offer much lower signal enhancements. In this study, we demonstrate the detection of signals from non-protonated 17 O in materials containing silicon. The sensitivity boost that made the experiment possible originates from three sources: indirect DNP excitation of 29 Si via protons, indirect detection of 17 O through 29 Si nuclei using two-dimensional 29 Si{17 O} D-HMQC, and Carr-Purcell-Meiboom-Gill refocusing of 29 Si magnetization during acquisition. This 29 Si-detected scheme enabled, for the first time, 2D 17 O-29 Si heteronuclear correlation spectroscopy in mesoporous silica and silica-alumina surfaces at natural abundance. In contrast to the silanols showing motion-averaged 17 O signals, the framework oxygens exhibit unperturbed powder patterns as unambiguous fingerprints of surface sites. Along with hydroxyl oxygens, detection of these moieties will help in gaining more atomistic-scale insights into surface chemistry.

17 O solid-state NMR at ultrahigh magnetic field of 35.2 T: Resolution of inequivalent oxygen sites in different phases of MOF MIL-53(Al).

MIL-53(Al) is a member of the most extensively studied metal-organic framework (MOF) families owing to its "flexible" framework and superior stability. 17 O solid-state NMR (SSNMR) spectroscopy is an ideal site-specific characterization tool as it probes local oxygen environments. Because oxygen local structure is often altered during phase change, 17 O SSNMR can be used to follow phase transitions. However, 17 O is a challenging nucleus to study via SSNMR due to its low sensitivity and resolution arising from the very low natural abundance of 17 O isotope and its quadrupolar nature. In this work, we describe that by using 17 O isotopic enrichment and performing 17 O SSNMR experiments at an ultrahigh magnetic field of 35.2 T, all chemically and crystallographically inequivalent oxygen sites in two representative MIL-53(Al) (as-made and water adsorbed) phases can be completely resolved. The number of signals in each phase is consistent with that predicted from the space group refined from powder X-ray diffraction data. The 17 O 1D magic-angle spinning (MAS) and 2D triple-quantum MAS (3QMAS) spectra at 35.2 T furnish fine information about the host-guest interactions and the structural changes associated with phase transition. The ability to completely resolve multiple chemically and crystallographically inequivalent oxygen sites in MOFs at very high magnetic field, as illustrated in this work, significantly enhances the potential for using the NMR crystallography approach to determine crystal structures of new MOFs and verify the structures of existing MOFs obtained from refining powder X-ray diffraction data.

Review on Applications of 17O in Hydrological Cycle.

The triple oxygen isotopes (16O, 17O, and 18O) are very useful in hydrological and climatological studies because of their sensitivity to environmental conditions. This review presents an overview of the published literature on the potential applications of 17O in hydrological studies. Dual-inlet isotope ratio mass spectrometry and laser absorption spectroscopy have been used to measure 17O, which provides information on atmospheric conditions at the moisture source and isotopic fractionations during transport and deposition processes. The variations of δ17O from the developed global meteoric water line, with a slope of 0.528, indicate the importance of regional or local effects on the 17O distribution. In polar regions, factors such as the supersaturation effect, intrusion of stratospheric vapor, post-depositional processes (local moisture recycling through sublimation), regional circulation patterns, sea ice concentration and local meteorological conditions determine the distribution of 17O-excess. Numerous studies have used these isotopes to detect the changes in the moisture source, mixing of different water vapor, evaporative loss in dry regions, re-evaporation of rain drops during warm precipitation and convective storms in low and mid-latitude waters. Owing to the large variation of the spatial scale of hydrological processes with their extent (i.e., whether the processes are local or regional), more studies based on isotopic composition of surface and subsurface water, convective precipitation, and water vapor, are required. In particular, in situ measurements are important for accurate simulations of atmospheric hydrological cycles by isotope-enabled general circulation models.

Electrophilicity Scale of Activated Amides: 17 O†NMR and 15 N†NMR Chemical Shifts of Acyclic Twisted Amides in N-C(O) Cross-Coupling.

The structure and properties of amides are of tremendous interest in organic synthesis and biochemistry. Traditional amides are planar and the carbonyl group non-electrophilic due to nN →π*C=O conjugation. In this study, we report electrophilicity scale by exploiting 17 O NMR and 15 N NMR chemical shifts of acyclic twisted and destabilized acyclic amides that have recently received major attention as precursors in N-C(O) cross-coupling by selective oxidative addition as well as precursors in electrophilic activation of N-C(O) bonds. Most crucially, we demonstrate that acyclic twisted amides feature electrophilicity of the carbonyl group that ranges between that of acid anhydrides and acid chlorides. Furthermore, a wide range of electrophilic amides is possible with gradually varying carbonyl electrophilicity by steric and electronic tuning of amide bond properties. Overall, the study quantifies for the first time that steric and electronic destabilization of the amide bond in common acyclic amides renders the amide bond as electrophilic as acid anhydrides and chlorides. These findings should have major implications on the fundamental properties of amide bonds.