Synthesis of Perdeuterated Alkyl Amines/Amides with Pt/C as Catalyst under Mild Conditions.

A convenient method for the synthesis of perdeuterated alkyl amides/amines is disclosed. Perdeuterated acetyl amides can be achieved by a hydrogen-deuterium (H/D) exchange protocol with Pt/C as a catalyst and D2O as a deuterium source under mild conditions. After removal or reduction of the acetyl group, this protocol can provide perdeuterated primary, secondary, and tertiary amines, which are difficult to achieve via other methods.

Revealing the Marine Cycles of Volatile Sulfur Compounds and Their Biogeochemical Controls: A Case of the Western North Pacific.

Volatile sulfur compounds, such as dimethyl sulfide (DMS), carbonyl sulfide (OCS), and carbon disulfide (CS2), have significant implications for both atmospheric chemistry and climate change. Despite the crucial role of oceans in regulating their atmospheric budgets, our comprehension of their cycles in seawater remains insufficient. To address this gap, a field investigation was conducted in the western North Pacific to clarify the sources, sinks, and biogeochemical controls of these gases in two different marine environments, including relatively eutrophic Kuroshio-Oyashio extension (KOE) and oligotrophic North Pacific subtropical gyre. Our findings revealed higher concentrations of these gases in both seawater and the atmosphere in the KOE compared to the subtropical gyre. In the KOE, nutrient-rich upwelling stimulated rapid DMS biological production, while reduced seawater temperatures hindered the removal of OCS and CS2, leading to their accumulation. Furthermore, we have quantitatively evaluated the relative contribution of each pathway to the source and sink of DMS, OCS, and CS2 within the mixed layer and identified vertical exchange as a potential sink in most cases, transporting substantial amounts of these gases from the mixed layer to deeper waters. This research advances our understanding of sulfur gas source-sink dynamics in seawater, contributing to the assessment of their marine emissions and atmospheric budgets.

Important Roles and Formation of Atmospheric Organosulfates in Marine Organic Aerosols: Influence of Phytoplankton Emissions and Anthropogenic Pollutants.

Organosulfates (OSs) could be potentially important compounds in marine organic aerosols, while their formation in marine atmospheres is far from clear due to a lack of cruise observations. In this work, shipboard atmospheric observations were conducted over the Yellow Sea and Bohai Sea to investigate the abundance and formation of biogenic isoprene/monoterpene-OSs in marine aerosols. The quantified OSs and NOSs accounted for 0.04-6.9% of marine organic aerosols and were 0.07-2.2% of the non-sea-salt (nss) sulfate in terms of sulfur content. Isoprene-related (nitrooxy-)OSs occupied 27-87% of the total quantified OSs, following the abundance order of summer > autumn > spring or winter. This order was driven by the marine phytoplankton biomass and sea surface temperature (SST), which controlled the seawater and atmospheric isoprene concentration levels. Under the severe impacts of anthropogenic pollutants from the East Asia continent in winter, monoterpene nitrooxy-OSs, generated with NOx involved in, increased to 34.4 ± 35.5 ng/m3 and contributed 68% of the quantified (nitrooxy-)OSs. Our results highlight the notable roles of biogenic OSs in marine organic aerosols over regions with high biological activity and high SST. The formation of biogenic OSs and their roles in altering marine aerosol properties calls for elaboration through cruise observations in different marine environments.

Contrasting effects of different light regimes on the photoreactivities of allochthonous and autochthonous chromophoric dissolved organic matter.

Chromophoric dissolved organic matter (CDOM) plays an important role in ultraviolet (UV) light absorption in the ocean. CDOM is known to originate from either an allochthonous or autochthonous source and has varying compositions and levels of reactivity; however, the effects of individual radiation treatments and the combined effects of UVA and UVB on allochthonous and autochthonous CDOM remain poorly understood. Thus, here, we measured changes in the common optical properties of CDOM collected from China's marginal seas and the Northwest Pacific, using full-spectrum, UVA (315-400 nm), and UVB (280-315 nm) irradiation to induce photodegradation over the same time period (60 h). Excitation-emission matrices (EEMs) combined with parallel factor analysis (PARAFAC) identified four components: marine humic-like C1, terrestrial humic-like C2, soil fulvic-like C3, and tryptophan-like C4. Although the behaviours of these components during full-spectrum irradiation exhibited similar decreasing tendencies, three components (C1, C3, and C4) underwent direct photodegradation under UVB exposure, whereas C2 was more susceptible to UVA degradation. The diverse photoreactivities of the source-dependent components to different light treatments led to differing photochemical behaviours of other optical indices [aCDOM(355), aCDOM(254), SR, HIX, and BIX]. The results indicate that irradiation preferentially reduced the high humification degree or humic substance content of allochthonous DOM, and promoted the transformation from the allochthonous humic DOM components to recently produced components. Although values for the samples from different sources overlapped frequently, principal component analysis (PCA) indicated that the overall optical signatures could be linked to the original CDOM source features. The degradation of CDOM humification, aromaticity, molecular weight, and autochthonous fractions under exposure can drive the CDOM biogeochemical cycle in marine environments. These findings can aid in a better understanding of the effects of different combinations of light treatments and CDOM characteristics on CDOM photochemical processes.

K2CO3/18-Crown-6-Catalyzed Selective H/D Exchange of Heteroarenes with Bromide as a Removable Directing Group.

The K2CO3/18-crown-6-catalyzed H/D exchange of heretoarenes in high atom % deuterium incorporation is disclosed. The use of a weak base as a catalyst leads to excellent site selectivity and broad functional group tolerance. Control experiments indicated that the use of bromide, which enhances the adjacent C-H bond reactivity, as a removable directing group is essential. Moreover, conversion of bromide to other functional groups is also performed to construct other useful deuterated compounds.

Characteristics and emissions of isoprene and other non-methane hydrocarbons in the Northwest Pacific Ocean and responses to atmospheric aerosol deposition.

Field investigations in the Northwest Pacific Ocean were carried out to determine the distributions of marine and atmospheric non-methane hydrocarbons (NMHCs), sources and environmental effects. We also conducted deck incubation experiments to investigate the effects of atmospheric aerosol deposition on NMHCs production. The marine NMHCs displayed an increasing trend from the South Equatorial Current to the Oyashio Current. The enhanced phytoplankton biomass and dissolved organic materials (DOM) content in the Kuroshio-Oyashio Extension contributed significantly to isoprene and NMHCs production compared with those in tropical waters and the North Pacific subtropical gyre. The Northwest Pacific Ocean was a significant source of atmospheric NMHCs, with average sea-to-air fluxes of 28.0 ± 38.9, 65.2 ± 73.3, 21.0 ± 26.7, 48.7 ± 62.6, 12.7 ± 15.9, 14.2 ± 16.8, and 41.7 ± 80.4 nmol m-2 d-1 for ethane, ethylene, propane, propylene, i-butane, n-butane, and isoprene, respectively. Influenced by seawater release and OH radical consumption, the atmospheric NMHCs apart from isoprene displayed upward trends with increasing latitude. The deck incubation showed that the addition of aerosols and acidic aerosols significantly boosted phytoplankton biomass, altered community structure, and accelerated the production of isoprene. However, the other six NMHCs showed no obvious responses to atmospheric aerosol deposition in the incubation experiments. In summary, ocean current movements and atmospheric deposition could influence the production and release of isoprene in the Northwest Pacific Ocean.

Biogeochemical controls on climatically active gases and atmospheric sulfate aerosols in the western Pacific.

The Pacific Ocean plays an important role in regulating the budget of climatically active gases and the burden of sulfate aerosols. Here, a field investigation was conducted to clarify the key processes and factors controlling climatically active gases, including dimethyl sulfide (DMS), carbonyl sulfide (OCS), carbon disulfide (CS2), and carbon dioxide (CO2), in both surface seawater and the lower atmosphere of the western Pacific. In addition, the relative contributions of different sources to atmospheric sulfate aerosols were quantitatively estimated, and their causes were explored. The maximum concentrations of DMS, OCS and CS2 and the minimum partial pressure of CO2 (pCO2) were observed in the Kuroshio-Oyashio Extension. Kuroshio-induced mesoscale eddies brought abundant nutrients and organic matter from the subsurface layer of Oyashio into the euphotic layer, thus enhancing primary productivity and accelerating the photoreaction of organic matter. These processes led to higher concentrations of DMS, OCS and CS2 and lower pCO2. However, the oligotrophic subsurface layer in the subtropical gyre and the strong barrier layer in the equatorial waters suppressed the upward fluxes of nutrients and organic matter, resulting in lower surface concentrations of DMS, OCS, and CS2 in these areas. Being far from the continents, atmospheric concentrations of DMS, OCS and CS2 and pCO2 in the western Pacific generally were observed to depend on the local sea-to-air exchange and may be regulated by atmospheric oxidation and mixing of air masses. In general, oceanic DMS emissions played an important role in the formation of sulfate aerosols in the western Pacific (accounting for ∼19.5% of total sulfate aerosols), especially in the Kuroshio-Oyashio Extension (∼32.3%). These processes in seawater may also determine the variations and emissions of other climatically active gases from biogenic and photochemical sources.

Aerobic oxidation of methane significantly reduces global diffusive methane emissions from shallow marine waters.

Methane is supersaturated in surface seawater and shallow coastal waters dominate global ocean methane emissions to the atmosphere. Aerobic methane oxidation (MOx) can reduce atmospheric evasion, but the magnitude and control of MOx remain poorly understood. Here we investigate methane sources and fates in the East China Sea and map global MOx rates in shallow waters by training machine-learning models. We show methane is produced during methylphosphonate decomposition under phosphate-limiting conditions and sedimentary release is also source of methane. High MOx rates observed in these productive coastal waters are correlated with methanotrophic activity and biomass. By merging the measured MOx rates with methane concentrations and other variables from a global database, we predict MOx rates and estimate that half of methane, amounting to 1.8 ± 2.7 Tg, is consumed annually in near-shore waters (<50 m), suggesting that aerobic methanotrophy is an important sink that significantly constrains global methane emissions.

Synthesis of ß-Deuterated Amino Acids via Palladium-Catalyzed H/D Exchange.

Despite several synthetic approaches that have been developed for α-deuterated amino acids, the synthesis of ß-deuterated amino acids has remained a challenge. Herein, we disclose a palladium catalyzed H/D exchange protocol for a ß-deuterated N-protected amino amide, which can be converted to a ß-deuterated amino acid simply by removal of protecting groups. This protocol is highly efficient, simply manipulated, and appliable for deuterium-labeling of many amino amides. In addition, deuterium labeling of phenylalanine derivatives was also successful when pivalic acid served as an additive to promote the H/D exchange process.

Silver salt enabled H/D exchange at the ß-position of thiophene rings: synthesis of fully deuterated thiophene derivatives.

We disclose a silver catalyzed H/D exchange reaction, which can introduce the deuterium atom at the ß position of thiophene rings without the assistance of any coordinating groups. The advantages of this reaction include operation in open air, usage of D2O as the deuterium source, good tolerance to a range of functional groups and obtaining high atom% deuterium incorporation. In addition, this H/D exchange reaction is employed for direct deuteration of a thiophene based monomer, which is usually prepared by multistep synthesis from expensive deuterated starting materials.

C-H Bond Functionalization of (Hetero)aryl Bromide Enabled Synthesis of Brominated Biaryl Compounds.

Aryl bromide is one of the most important compounds in organic chemistry, because it is widely used as synthetic building blocks enabling quick access to a wide array of bioactive molecules, organic materials, and polymers via the versatile cutting-edge transformations of C-Br bond. Direct C-H bond functionalization of aryl bromide is considered to be an efficient way to prepare functionalized aryl bromides; however, it is rarely explored possibly due to the relatively low reactivity of aryl bromide toward C-H bond activation. We herein report a palladium-catalyzed coupling reaction between aryl iodide and aryl bromide for preparing brominated biaryl compounds via a silver-mediated C-H bond activation pathway.

Seasonality of dimethylated sulfur compounds cycling in north China marginal seas.

Dimethylated sulfur compounds play an important role in global sulfur cycle. We investigated the seasonality of dimethylsulfoniopropionate (DMSP), dimethylsulfoxide (DMSO), dimethylsulfide (DMS) and associated processes in two north China marginal seas during 2014 and 2016. High concentrations of DMS, DMSP and DMSO occurred in summer/spring, while the lowest were observed in winter. This clear seasonality was primarily driven by biomass abundance and phytoplankton communities, reflected in chlorophyll a concentrations and the composition/ratios of diatoms and dinoflagellates. The spring maximum was attributed to the annual occurrence of algal bloom. The sea-to-air fluxes of DMS also varied largely between seasons, with an average of 8.84, 11.87, 10.50 and 2.14 µmol m-2 day-1 in spring, summer, autumn and winter, respectively. Given the seasonal uncertainty of sea-to-air flux, the seasonality or situations where specific blooms occur regularly should be considered for accurate estimation of annual global DMS emission.

Controlling factors of annual cycle of dimethylsulfide in the Yellow and East China seas.

We developed a dimethylsulfide (DMS) module coupled to an ecological dynamics model studying the annual DMS cycle of the Yellow and East China seas (YECS). The model results showed that surface DMS concentrations ([DMS]) peaked in August along the coast, and there exhibited several DMS peaks offshore annually. In addition, surface [DMS] were higher in the Yellow Sea than that in the East China Sea. The annual mean surface [DMS] of the YECS reached to 4.55 nmol/L, and oceanic DMS emissions from this sea area was 6.78 µmol/(m2 day). Several sensitivity experiments demonstrated that phytoplankton community and sea water temperature exerted crucial effects on seasonal variations of surface [DMS]; and phytoplankton community or temperature changed the timing of surface DMS peak while photolysis affected the magnitude of [DMS]. Moreover, the effect size of phytoplankton community or water temperature varied spatially.

Synthesis of Multideuterated (Hetero)aryl Bromides by Ag(I)-Catalyzed H/D Exchange.

Deterium-labeled (hetero)aryl bromide is one of the most widespread applicable motifs to achieve important deuterated architectures for various scientific applications. Traditionally, these deterium-labeled (hetero)aryl bromides are commonly prepared via multistep syntheses. Herein, we disclose a direct H/D exchange protocol for deuteration of (hetero)aryl bromides using Ag2CO3 as catalyst and D2O as deuterium source. This protocol is highly efficient, simply manipulated, and appliable for deuterium-labeling of over 55 (hetero)aryl bromides including bioactive druglike molecules and key intermediates of functional materials. In addition, this method showed distinguishing site-selectivity toward the existing transition-metal-catalyzed HIE process, leading to multideuterated (hetero)aryl bromides in one step.

Emissions and potential controls of light alkenes from the marginal seas of China.

Marine-derived reactive gases constitute a substantial fraction of volatile organic compounds and directly impact atmospheric chemistry and the global climate. Light alkene emissions from marginal seas are limited, and their contribution to atmospheric concentrations is likely underestimated. We surveyed oceanic emissions of ethylene, propylene, and isoprene, as well as their potential controlling factors in the marginal seas of China during the cruises in 2014-2015. Significant temporal-spatial variations in ethylene, propylene, and isoprene concentrations were observed, with the highest occurring in summer near the coastal regions. Isoprene concentrations were primarily controlled by phytoplankton biomass (i.e., Chl-a) in coastal regions, while the elevated concentrations of ethylene and propylene were attributed to photochemical reactions with the high levels of dissolved organic matter (DOM). Additionally, the vertical distributions of ethylene and propylene mirrored light penetration, with exponential decrease in concentrations with depth. However, there were high values of ethylene and propylene observed at deep chlorophyll maximum, suggesting the existence of non-photochemical production pathways, most likely biological origin. Emissions of ethylene, propylene, and isoprene from the marginal seas of China were estimated to be 0.022, 0.024, and 0.011 Tg C yr-1, respectively, indicating they are important contributors to global non-methane hydrocarbons. Due to the scarcity of alkene emission data for marginal seas, current global emissions have been underestimated to some extent. It is essential to incorporate the contributions from marginal seas to accurately estimate alkene budgets on global scales.

Occurance, emission and environmental effects of non-methane hydrocarbons in the Yellow Sea and the East China Sea.

The spatial distributions, fluxes, and environmental effects of non-methane hydrocarbons (NMHCs) were investigated in the Yellow Sea (YS) and the East China Sea (ECS) in spring. The average concentrations of ethane, propane, i-/n-butane, ethylene, propylene and isoprene in the seawater were 18.1 ± 6.4, 15.4 ± 4.7, 6.8 ± 2.9, 6.4 ± 3.2, 67.1 ± 26.7, 20.5 ± 8.7 and 17.1 ± 11.1 pmol L-1, respectively. The alkenes in the surface seawater were more abundant than their saturated homologs and NMHCs concentrations (with the exception of isoprene) decreased with carbon number. The spatial variations of isoprene were consistent with the distributions of chlorophyll a (Chl-a) and Chaetoceros, Skeletonema, Nitzschia mainly contributed to the production of isoprene, while the others' distributions might be related to their photochemical production. Observations in atmospheric NMHCs indicated alkanes in the marine atmosphere decreased from inshore to offshore due to influence of the continental emissions, while alkenes were largely derived from the oceanic source. In addition, no apparent diurnal discrepancy of atmospheric NMHCs (except for isoprene) were found between daytime and night. As the main sink of NMHCs in seawater, the average sea-to-air fluxes of ethane, propane, i-/n-butane, ethylene and propylene were 31.70, 29.75, 18.49, 15.89, 239.6, 67.94 and 52.41 nmol m-2 d-1, respectively. The average annual emissions of isoprene accounted for 0.1-1.3% of the global ocean emissions, which indicated that the coastal and shelf areas might be significant sources of isoprene. Furthermore, this study represents the first effort to estimate the environmental effects caused by NMHCs over the YS and the ECS and the results demonstrated contributions of alkanes to ozone and secondary organic aerosol (SOA) formation were lower than those of the alkenes and the largest contributor was isoprene.

Central deficiency of norepinephrine synthesis and norepinephrinergic neurotransmission contributes to seizure-induced respiratory arrest.

Sudden unexpected death in epilepsy (SUDEP) is the leading cause of mortality in patients with intractable epilepsy. However, the pathogenesis of SUDEP seems to be poorly understood. Our previous findings showed that the incidence of seizure-induced respiratory arrest (S-IRA) was markedly reduced by atomoxetine in a murine SUDEP model. Because the central norepinephrine α-1 receptor (NEα-1R) plays a vital role in regulating respiratory function, we hypothesized that the suppression of S-IRA by atomoxetine was mediated by NE/NEα-1R interactions that can be reversed by NEα-1R antagonism. We examined whether atomoxetine-mediated suppression of S-IRA evoked by either acoustic stimulation or pentylenetetrazole (PTZ) in DBA/1 mice can be reversed by intraperitoneal (IP) and intracerebroventricular (ICV) administration of prazosin, a selective antagonist of NEα-1R. The content and activity of tyrosine hydroxylase (TH), a rate-limiting enzyme for NE synthesis, in the lower brainstem was measured by ELISA. Electroencephalograms (EEG) were obtained from using the PTZ-evoked SUDEP model. In our models, atomoxetine-mediated suppression of S-IRA evoked by either acoustic stimulation or PTZ was significantly reversed by low doses of IP and ICV prazosin. Neither repetitive acoustic stimulation nor S-IRA reduced TH levels in lower brainstem. However, the enzyme activity of TH levels in lower brainstem was significantly increased by mechanical ventilation with DBA/1 mice, which makes the dying DBA/1 mice suffering from S-IRA and SUDEP recover. EEG data showed that although the protective effect of atomoxetine was reversed by prazosin, neither drug suppressed EEG activity. These data suggest that deficient synthesis of NE and norepinephrinergic neurotransmission contributed to S-IRA and that the NEα-1R is a potential therapeutic target for the prevention of SUDEP.

Bacteria are important dimethylsulfoniopropionate producers in marine aphotic and high-pressure environments.

Dimethylsulfoniopropionate (DMSP) is an important marine osmolyte. Aphotic environments are only recently being considered as potential contributors to global DMSP production. Here, our Mariana Trench study reveals a typical seawater DMSP/dimethylsulfide (DMS) profile, with highest concentrations in the euphotic zone and decreased but consistent levels below. The genetic potential for bacterial DMSP synthesis via the dsyB gene and its transcription is greater in the deep ocean, and is highest in the sediment.s DMSP catabolic potential is present throughout the trench waters, but is less prominent below 8000 m, perhaps indicating a preference to store DMSP in the deep for stress protection. Deep ocean bacterial isolates show enhanced DMSP production under increased hydrostatic pressure. Furthermore, bacterial dsyB mutants are less tolerant of deep ocean pressures than wild-type strains. Thus, we propose a physiological function for DMSP in hydrostatic pressure protection, and that bacteria are key DMSP producers in deep seawater and sediment.

Ag(i)-Mediated hydrogen isotope exchange of mono-fluorinated (hetero)arenes.

An efficient approach to install deuterium into mono-fluorinated (hetero)arenes by a Ag2CO3/Sphos-mediated HIE protocol with D2O as the deuterium source has been disclosed. This method showed a specific site selectivity of deuteration at the α-position of the fluorine atom, which is complementary to the existing transition metal-catalyzed HIE process.