CO2 Sensitivity Research Articles

Green manure application accelerates soil organic carbon stock loss under plastic film mulching

This study investigated the offset effect between green manure (GM) application and plastic film mulching (PFM) on soil organic carbon (SOC) stock change during maize cultivation. Within PFM and no-mulching treatments, three different fertilization sub-treatments were applied: (a) chemical fertilizer, (b) barley and (c) hairy vetch. The SOC balance were evaluated by analyzing the net ecosystem carbon budget (NECB). The results showed that the NECB value was negative during maize cultivation regardless of mulching or fertilization condition, indicated SOC loss. The PFM increased maize yield (P < 0.001) by improved soil moisture and temperature. Crop growth was enhanced under PFM relative to no mulching by 23–26%, 16–25% and 1–8% in the sub-treatments, respectively. However, PFM significantly increased carbon losses by 26–29%, 103–107% and 60–62% over no mulching in each fertilization, respectively (P < 0.001). the temperature sensitivity of CO2–C loss was 52–70% higher in PFM than that in no mulching. Accordingly, the NECB was 1.3, 5.6 and 3.0 times lower with PFM relative to the no-mulching value in the three fertilization, respectively. Under no mulching, GM application reduced SOC loss by 33–59% compared with NPK, while under PFM, it accelerated SOC loss by 8–48%. Barley showed the smallest NECB decrease (− 1.0 Mg C ha−1) under no mulching and the largest NECB decrease (− 5.7 Mg C ha−1) under PFM. The findings indicate that GM application is not enough to sustain SOC stock under PFM and suggest that the additional recycling of crop residue, such as maize stover, is necessary to increase the soil C stock.

Variation in the onset of CO2-induced anxiety in female Sprague Dawley rats

Carbon dioxide (CO2) is commonly used to kill laboratory rats. Rats find CO2 aversive and aversion varies between individuals, indicating that rats vary in CO2 sensitivity. Healthy humans experience feelings of anxiety at concentrations similar to those avoided by rats, and these feelings are diminished by the administration of benzodiazepines. Our aim was to assess the effects of the benzodiazepine midazolam on individual thresholds of rat aversion to CO2. Six female Sprague Dawley rats were repeatedly exposed to CO2 gradual-fill in approach-avoidance testing. The first three exposures were to a control-treatment followed by three exposures to midazolam (0.375 mg/kg). Within each treatment aversion to CO2 was not affected by exposure number; however, tolerance increased from an average of 10.7% CO2 avoided during control sessions, to 15.5% CO2 avoided when treated with midazolam. These results indicate that rats experience anxiety when exposed to CO2, and that variation in rat CO2 sensitivity is driven by individual differences in the onset of these feelings of anxiety. No rat tolerated CO2 concentrations required to induce loss of consciousness.

Modification of Carbon Nitride/Reduced Graphene Oxide van der Waals Heterostructure with Copper Nanoparticles To Improve CO2 Sensitivity.

Carbon nitride/reduced graphene oxide (rGO) van der Waals heterostructures (vdWH) have previously shown exceptional oxygen sensitivity via a photoredox mechanism, making it a potential material candidate for various applications such as oxygen reduction reaction catalysis and oxygen sensing. In this work, the electronic structure of a carbon nitride/rGO composite is modified through the introduction of copper nanoparticles (NPs). When incorporated into a chemiresistor device, this vdWH displayed a newfound CO2 sensitivity. The effects of humidity and light were investigated and found to be crucial components for the CO2 sensitivity. Density functional theory calculations performed on a carbon nitride/copper NP@rGO model system found an enhanced stabilization of CO2 caused by H-bonds between the carbon nitride layer and chemisorbed CO2 on copper, pointing to the important role played by humidity. The synergetic effect between the carbon nitride layer interfaced with CuNP@rGO, in combination with humidity and light (395 nm) irradiation, is found to be responsible for the newfound sensitivity toward CO2.

Alkylamine-Integrated Metal-Organic Framework-Based Waveguide Sensors for Efficient Detection of Carbon Dioxide from Humid Gas Streams.

Metal-organic framework (MOF)-based chemical sensors have recently been demonstrated to be highly selective, sensitive, and reversible for CO2 sensing across a range of platforms including optical fiber and surface acoustic wave-based sensors. However, interference of water molecules is a primary issue in CO2 sensing systems based upon MOF layers due to cross-sensitivity, stability of MOF-based materials in humid conditions, and associated baseline drift over the lifetime of sensors. Herein, we develop a simple approach of alleviating the negative effect of water vapor to the optical fiber sensor by using alkylamine (i.e., oleylamine) to form a protective hydrophobic layer on the surface of MOFs for improving water stability.Alkylamine-modification of a MOF-coatedoptical fiber sensor provides a reversible and stable sensing response to a wide range of CO2 concentrations while also enhancing the CO2 sensitivity of the sensor under wet conditions. The FT-IR and breakthrough studies on the oleylamine-modified MOF confirm that the water vapor does not adversely impact the intrinsic CO2 sorption capacities. Thus, this simple stratrgy for enhancing the CO2/H2O selectivity in the MOF sorbent could also be useful for improving CO2 capture/separation performance in flue gas stream.

A highly fluorescent post-modified metal organic framework probe for selective, reversible and rapid carbon dioxide detection

The monitoring of the arterial and exhaled CO2 is of great importance. Despite of many reports on metal organic frameworks (MOFs) in adsorbing and separating CO2, the application of fluorescent MOFs probes for CO2 detection was rarely reported. A new fluorescent MOF probe UIO-66-ONa for CO2 detection was developed via post-synthesis of UIO-66-NH2 through a Schiff base reaction with salicylaldehyde and further treatment with sodium hydroxide. This probe exhibited a remarkable fluorescence color change from green to blue and showed excellent sensitivity and selectivity for CO2 sensing in solution. The detection limit was as low as 3.5 × 10−7 M. The excellent sensing performance of UIO-66-ONa was ascribed to the efficient reaction between sodium phenolic group and CO2, which led to the transformation of UIO-66-ONa to UIO-66-OH as evidenced by the emission spectra. This post-synthetic modification idea provided a new strategy for designing fluorescent MOFs probes for CO2 detection.

Cx26 keratitis ichthyosis deafness syndrome mutations trigger alternative splicing of Cx26 to prevent expression and cause toxicity in vitro.

The Cx26 mRNA has not been reported to undergo alternative splicing. In expressing a series of human keratitis ichthyosis deafness (KID) syndrome mutations of Cx26 (A88V, N14K and A40V), we found the production of a truncated mRNA product. These mutations, although not creating a cryptic splice site, appeared to activate a pre-existing cryptic splice site. The alternative splicing of the mutant Cx26 mRNA could be prevented by mutating the predicted 3′, 5′ splice sites and the branch point. The presence of a C-terminal fluorescent protein tag (mCherry or Clover) was necessary for this alternative splicing to occur. Strangely, Cx26A88V could cause the alternative splicing of co-expressed WT Cx26—suggesting a trans effect. The alternative splicing of Cx26A88V caused cell death, and this could be prevented by the 3′, 5′ and branch point mutations. Expression of the KID syndrome mutants could be rescued by combining them with removal of the 5′ splice site. We used this strategy to enable expression of Cx26A40V-5′ and demonstrate that this KID syndrome mutation removed CO2 sensitivity from the Cx26 hemichannel. This is the fourth KID syndrome mutation found to abolish the CO2-sensitivity of the Cx26 hemichannel, and suggests that the altered CO­2-sensitivity could contribute to the pathology of this mutation. Future research on KID syndrome mutations should take care to avoid using a C-terminal tag to track cellular localization and expression or if this is unavoidable, combine this mutation with removal of the 5′ splice site.

Sensitivity of atmospheric CO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; to regional variability in particulate organic matter remineralization depths

Abstract. The concentration of CO2 in the atmosphere is sensitive to changes in the depth at which sinking particulate organic matter is remineralized: often described as a change in the exponent “b” of the Martin curve. Sediment trap observations from deep and intermediate depths suggest there is a spatially heterogeneous pattern of b, particularly varying with latitude, but disagree over the exact spatial patterns. Here we use a biogeochemical model of the phosphorus cycle coupled with a steady-state representation of ocean circulation to explore the sensitivity of preformed phosphate and atmospheric CO2 to spatial variability in remineralization depths. A Latin hypercube sampling method is used to simultaneously vary the Martin curve independently within 15 different regions, as a basis for a regression-based analysis used to derive a quantitative measure of sensitivity. Approximately 30 % of the sensitivity of atmospheric CO2 to changes in remineralization depths is driven by changes in the subantarctic region (36 to 60∘ S) similar in magnitude to the Pacific basin despite the much smaller area and lower export production. Overall, the absolute magnitude of sensitivity is controlled by export production, but the relative spatial patterns in sensitivity are predominantly constrained by ocean circulation pathways. The high sensitivity in the subantarctic regions is driven by a combination of high export production and the high connectivity of these regions to regions important for the export of preformed nutrients such as the Southern Ocean and North Atlantic. Overall, regionally varying remineralization depths contribute to variability in CO2 of between around 5 and 15 ppm, relative to a global mean change in remineralization depth. Future changes in the environmental and ecological drivers of remineralization, such as temperature and ocean acidification, are expected to be most significant in the high latitudes where CO2 sensitivity to remineralization is also highest. The importance of ocean circulation pathways to the high sensitivity in subantarctic regions also has significance for past climates given the importance of circulation changes in the Southern Ocean.

On-Chip Tailorability of Capacitive Gas Sensors Integrated with Metal-Organic Framework Films.

Gas sensing technologies for smart cities require miniaturization, cost-effectiveness, low power consumption, and outstanding sensitivity and selectivity. On-chip, tailorable capacitive sensors integrated with metal-organic framework (MOF) films are presented, in which abundant coordinatively unsaturated metal sites are available for gas detection. The in situ growth of homogeneous Mg-MOF-74 films is realized with an appropriate metal-to-ligand ratio. The resultant sensors exhibit selective detection for benzene vapor and carbon dioxide (CO2 ) at room temperature. Postsynthetic modification of Mg-MOF-74 films with ethylenediamine decreases sensitivity toward benzene but increases selectivity to CO2 . The reduced porosity and blocked open metal sites caused by amine coordination account for a deterioration in the sensing performance for benzene (by ca. 60 %). The enhanced sensitivity for CO2 (by ca. 25 %) stems from a tailored amine-CO2 interaction. This study demonstrates the feasibility of tuning gas sensing properties by adjusting MOF-analyte interactions, thereby offering new perspectives for the development of MOF-based sensors.

Effect of Woodchips Biochar on Sensitivity to Temperature of Soil Greenhouse Gases Emissions

Research Highlights: Biochar is the carbonaceous product of pyrolysis or the gasification of biomass that is used as soil amendment to improve soil fertility and increase soil carbon stock. Biochar has been shown to increase, decrease, or have no effect on the emissions of greenhouse gases (GHG) from soil, depending on the specific soil and biochar characteristics. However, the temperature sensitivity of these gas emissions in biochar-amended soils is still poorly investigated. Background and Objectives: A pot experiment was set up to investigate the impact of woodchips biochar on the temperature sensitivity of the main GHG (CO2, CH4, and N2O) emissions from soil. Materials and Methods: Nine pots (14 L volume) were filled with soil mixed with biochar at two application rates (0.021 kg of biochar/kg of soil and 0.042 kg of biochar/kg of soil) or with soil alone as the control (three pots per treatment). Pots were incubated in a growth chamber and the emissions of CO2, CH4, and N2O were monitored for two weeks with a cavity ring-down gas analyzer connected to three closed dynamic chambers. The temperature in the chamber increased from 10 °C to 30 °C during the first week and decreased back to 10 °C during the second week, with a daily change of 5 °C. Soil water content was kept at 20% (w/w). Results: Biochar application did not significantly affect the temperature sensitivity of CO2 and N2O emissions. However, the sensitivity of CH4 uptake from soil significantly decreased by the application of biochar, reducing the CH4 soil consumption compared to the un-amended soil, especially at high soil temperatures. Basal CO2 respiration at 10 °C was significantly higher in the highest biochar application rate compared to the control soil. Conclusions: These results confirmed that the magnitude and direction of the influence of biochar on temperature sensitivity of GHG emissions depend on the specific GHG considered. The biochar tested in this study did not affect soil N2O emission and only marginally affected CO2 emission in a wide range of soil temperatures. However, it showed a negative impact on soil CH4 uptake, particularly at a high temperature, having important implications in a future warmer climate scenario and at higher application rates.

Electrodeposited copper nanoparticles in ionic liquid microchannels electrode for carbon dioxide sensor

The modification of sensing surfaces is of great importance in many practical applications for various gas detections. High sensitivity is desired for the sensing surfaces of gas sensors, especially in a viscous electrolyte (e.g., room temperature ionic liquid), which has a relatively slow diffusion of analyte gas to electrode surface compared to conventional aqueous solvents. The enhancement of sensing surface sensitivity can be achieved in various strategies from chemical to electrochemical modification. In this work, ionic liquid (IL) based microchannels electrode surface was modified by electrodeposition of copper nanoparticles (CuNPs) and used for real-time carbon dioxide (CO2) sensing application via long-term chronoamperometry. The as-prepared IL-based CuNPs-microchannels electrode was characterized by optical microscope, energy dispersive X-ray analysis (EDX) and scanning electron microscope (SEM). The IL-based CuNPs-microchannels electrode sensors demonstrated excellent performance (high sensitivity and fast response time) for CO2 sensing with good linearity from 2.4% - 11% with the detection limits of 0.14%.

Chemiresistive Sensing of Ambient CO2 by an Autogenously Hydrated Cu3(hexaiminobenzene)2 Framework.

A growing demand for indoor atmosphere monitoring relies critically on the ability to reliably and quantitatively detect carbon dioxide. Widespread adoption of CO2 sensors requires vastly improved materials and approaches because selective sensing of CO2 under ambient conditions, where relative humidity (RH) and other atmosphere contaminants provide a complex scenario, is particularly challenging. This report describes an ambient CO2 chemiresistor platform based on nanoporous, electrically conducting two-dimensional metal–organic frameworks (2D MOFs). The CO2 chemiresistive sensitivity of 2D MOFs is attained through the incorporation of imino-semiquinonate moieties, i.e., well-defined N-heteroatom functionalization. The best performance is obtained with Cu3(hexaiminobenzene)2, Cu3HIB2, which shows selective and robust ambient CO2 sensing properties at practically relevant levels (400–2500 ppm). The observed ambient CO2 sensitivity is nearly RH-independent in the range 10–80% RH. Cu3HIB2 shows higher sensitivity over a broader RH range than any other known chemiresistor. Characterization of the CO2-MOF interaction through a combination of in situ optical spectroscopy and density functional theory calculations evidence autogenously generated hydrated adsorption sites and a charge trapping mechanism as responsible for the intriguing CO2 sensing properties of Cu3HIB2.

Thioglycolic acid-capped ZnSe quantum dots as nanoprobe for cobalt(II) and iron(III) via measurement of grey level, UV-vis spectra and dynamic light scattering.

Thioglycolic acid-functionalized ZnSe quantum dots (QDs) as a colorimetricnanoprobe were prepared and applied to the determination of cobalt(II) and iron(III). Test strips were obtained by a dipping-drying process. On exposure to Co(II), they undergo a color change from white to brown, and on exposure to Fe(III) from white to pink. The limits of detection (LOD) are 2.6mgL-1 for Co(II) and 2.2mgL-1 for Fe(III). Test strips introduce a low-cost, portable, rapid and convenient tool for determination of Co(II) and Fe(III). In addition, two other analytical methods have been studied for detection of Co(II) and Fe(III) at low concentration. The first is UV-vis spectrometry which has a LOD as low as 0.14mgL-1 for Co(II) (at 412nm) and 0.12mgL-1 for Fe(III) (at 400nm). The second is dynamic light scattering (DLS) with a LOD of 3.0μgL-1 for Co(II) and 2.5μgL-1 for Fe(III). Graphical abstract Thioglycolic acid-functionalized ZnSe quantum dots (TGA-ZnSe QDs) show high sensitivity and low detection limits for Co2+ and Fe3+.

Development of a Wireless Surface Acoustic Wave Methane Sensor Using a Metal-Organic Framework As a Sensing Layer for Natural Gas Pipelines

Methane emission from the processing and transportation of fossil fuels can create serious environmental and safety issues as well as a financial burden. The need to monitor the energy infrastructure creates an opportunity for developing low-cost and robust sensors with wireless options. Wireless surface acoustic wave (SAW) devices, which are highly sensitive, cost-efficient, and passive, are a potential candidate for these applications. Nanoporous metal-organic frameworks (MOFs), which can selectively adsorb large amounts of gases in engineered pores at ambient conditions, are potential sensing layers. Here, we present on the development of a wireless and passive SAW sensor using the MOF zeolitic imidazolate framework-8 (ZIF-8) as the sensing layer for methane detection at ambient conditions. The SAW delay lines (nominal operating frequency = 436 MHz) were custom fabricated on Y-Z LiNbO3 piezoelectric substrates and coated with a 500 nm thick ZIF-8 layer using a dip coating method. The devices were excited by 428 MHz RF pulses to test for various concentrations of CO2 and CH4 in N2 background at a constant gas flow rate. Wireless measurements were performed via dipole antennas of nominal resonant frequency 433 MHz. When the sensor was exposed to the gases, surface acoustic wave phase shifted in a negative direction relative to the N2 baseline. This shift was attributed to the decrease in SAW velocity due to the increased mass of the MOF film upon gas adsorption. The CO2 and CH4 sensitivities extracted as the slopes of the respective calibration curves were 1.26 deg/vol-% and 0.03 deg/vol-%, respectively. It is important to note that currently tested minimum concentrations of CO2 and CH4 were 1% and 20%, respectively. Also, the wireless measurements were highly affected by the housing and metal reflectors around it. The demonstration on wireless methane sensing is of great importance for remote monitoring of methane emission sites and transmission pipelines. Our current investigations are focused in advancing the detection limit for leak detection and addressing the electromagnetic interferences in wireless measurement caused by the housing.

Evidence for consistent individual differences in rat sensitivity to carbon dioxide.

Carbon dioxide (CO2) gradual-fill is commonly used to kill laboratory rats, but this use remains controversial due to a lack of agreement between studies. Inconsistencies may arise from differences in behaviors measured (e.g. active versus passive behaviors), in how rats cope with threats, or in rat sensitivity to CO2. The aims of the current study were to 1) describe active and passive responses during CO2 forced exposure, 2) determine if these responses are consistent within individuals and across aversive stimuli, 3) assess individual differences in aversion to CO2 in aversion-avoidance and approach-avoidance tests and 4) determine how responses in aversion tests relate to individual differences in behavior during forced exposure. Twelve Sprague Dawley female rats were exposed twice to three treatments: CO2, oxygen (O2), and fox scent, and were exposed to CO2 twice in each aversion test. The change in behavior from baseline was higher for rearing and locomotion when rats were exposed to CO2 than when exposed to O2 and fox scent. Responses varied among rats but were consistent across multiple tests within rats. For example, rearing was consistent within individuals between two exposures to CO2. Similarly, the strength of aversion was consistent within individuals across multiple exposures to CO2 in aversion-avoidance and approach-avoidance testing. Latency to avoid CO2 in aversion-avoidance tests was negatively correlated with rearing during CO2 forced exposure. Collectively, these results indicate that rat responses to CO2 vary between (but are consistent within) individuals, suggesting that rats vary in CO2 sensitivity. However, even the less responsive rats avoided CO2 concentrations far below those necessary to achieve unconsciousness, indicating that all rats likely experience negative states when euthanized with CO2.

The Strength of Low-Cloud Feedbacks and Tropical Climate: A CESM Sensitivity Study

Abstract Variability in the strength of low-cloud feedbacks across climate models is the primary contributor to the spread in their estimates of equilibrium climate sensitivity (ECS). This raises the question: What are the regional implications for key features of tropical climate of globally weak versus strong low-cloud feedbacks in response to greenhouse gas–induced warming? To address this question and formalize our understanding of cloud controls on tropical climate, we perform a suite of idealized fully coupled and slab-ocean climate simulations across which we systematically scale the strength of the low-cloud-cover feedback under abrupt 2 × CO2 forcing within a single model, thereby isolating the impact of low-cloud feedback strength. The feedback strength is varied by modifying the stratus cloud fraction so that it is a function of not only local conditions but also global temperature in a series of abrupt 2 × CO2 sensitivity experiments. The unperturbed decrease in low cloud cover (LCC) under 2 × CO2 is greatest in the mid- and high-latitude oceans, and the subtropical eastern Pacific and Atlantic, a pattern that is magnified as the feedback strength is scaled. Consequently, sea surface temperature (SST) increases more in these regions as well as the Pacific cold tongue. As the strength of the low-cloud feedback increases this results in not only increased ECS, but also an enhanced reduction of the large-scale zonal and meridional SST gradients (structural climate sensitivity), with implications for the atmospheric Hadley and Walker circulations, as well as the hydrological cycle. The relevance of our results to simulating past warm climate is also discussed.

Isoprene Suppression by CO2 Is Not Due to Triose Phosphate Utilization (TPU) Limitation

Isoprene is one of the most abundant volatile organic compounds produced by some, though not all, plant species. It confers stress tolerance in both emitting and non-emitting species and has large impacts on gene regulation as well as on atmospheric chemistry. Understanding the control of isoprene emission from plants is important to understanding plant responses to future atmospheric conditions. In this study we determined that suppression of isoprene emission from plants by high CO2 concentrations is reduced but not eliminated by high temperature. We tested whether the CO2 suppression is caused by the reduction in ATP or NADPH availability caused by triose phosphate utilization (TPU) limitation of photosynthesis at high CO2. We measured CO2 assimilation as well as several photosynthetic electron transport parameters under multiple atmospheric conditions in four plant species grown at ambient CO2. While CO2 sensitivity of isoprene emission was somewhat correlated with TPU in some species, in other species it was not. Poplar exhibited significant CO2 suppression of isoprene emission but no evidence for TPU so we investigated further measuring the electrochromic shift that gives information on ATP synthesis and photosystem I oxidation state. In all cases photosynthetic parameters were unchanged while isoprene emission dropped in response to increasing CO2. Non-photorespiratory conditions (2% O2) led to an increase in isoprene emission at low CO2 but did not alleviate suppression by CO2. In all measured species the combination of higher temperature along with higher CO2 concentrations led to a net increase of isoprene emission in response to a moderate scenario for temperature and CO2 concentration in 2100 in the upper Midwest.

Acute hyperglycemia does not alter central respiratory CO2 chemoreflex responsiveness

The control of breathing is modulated by two distinct but interacting respiratory chemoreceptor compartments: peripheral chemoreceptors (PCRs; carotid bodies) and central chemoreceptors (CCRs; brainstem). The PCRs respond to variety of chemostimuli, including arterial oxygen, arterial carbon dioxide, glucose, insulin and temperature, and are now thought to act as metabolic sensors. However, CCRs have only been characterized as carbon dioxide/acid sensors (PCO2/[H+]). PCRs respond to chemostimulation faster than CCRs, which may mask CCR responses to stimuli like acute hyperglycemia. The aim of this study was to characterize the relationship between alterations in blood glucose concentration and central respiratory chemoreflex responsiveness via hyperoxic rebreathing in healthy humans. We hypothesized that experimentally‐induced relative hyperglycemia following an oral glucose tolerance test (OGTT; 75g, 300 ml) would (a) increase the rate of CO2 accumulation during rebreathing and (b) augment central respiratory chemoreflex responsiveness due to a synergistic effect of hyperglycemia on the CO2 sensitivity of CCR neurons. In 10 healthy participants, we measured minute ventilation (VI; L/min; pneumotachometer) and end‐tidal carbon dioxide (PETCO2; Torr; gas analyzer). We used the modified hyperoxic rebreathing test to isolate CCRs and quantify the central chemoreflex responsiveness to increases in metabolically‐derived CO2. Blood glucose levels were higher 30‐min following the OGTT beverage (i.e., glucose‐loaded) compared to fasted (7.8±1.1 vs. 4.7±0.4 mmol/L; P&lt;0.0001). During rebreathing, the rate of end‐tidal (PET)CO2 accumulation was greater in the glucose loaded trial compared to the fasted trial (0.086±0.007 vs. 0.07±0.008 vs. Torr/sec; P=0.0002). These findings confirm the hyperglycemic stimulation between trials. However, the central respiratory chemoreflex responsiveness during rebreathing was not different between glucose loaded and fasted trials (2.3±1.4 vs. 2.5±1.8 vs. L/min/Torr CO2; P=0.59). These preliminary findings suggest that relative hyperglycemia does not affect the central respiratory chemoreflex responsive to hyperoxic rebreathing. The CCRs may be a more specialized respiratory chemoreceptor, with a phenotype to detect only metabolically‐derived accumulations in CO2.Support or Funding InformationNSERC Discovery and MRU Faculty of Science and TechnologyThis abstract is from the Experimental Biology 2019 Meeting. There is no full text article associated with this abstract published in The FASEB Journal.

Mixed organic ligand-based colorimetric and ratiometric chemosensors for Co2+: structure-activity relationships.

In this work, chemosensors based on mixed ligands were proposed for the cooperative detection of Co2+. The relationship between the specifically selected mixed organic ligands and the detection activities is discussed. Diverse responses to metal ions can be tuned by controlling the structural features of organic ligands, such as different sizes, geometries, substituents, and connectivity. Among the nine investigated systems, DHAB-Tpy, DHAB-Phen, and DHAB-Dpa displayed high selectivity and sensitivity for Co2+, with detection limits of 4.5 × 10-7M, 1.1 × 10-7M, and 8.0 × 10-8M, respectively. The detection of Co2+ was not affected by other metal ions, anions, amino acids, proteins, nucleic acids, lipids and pH conditions. Furthermore, the proposed method was validated in the analysis of Co2+ in real water samples with satisfactory recovery and relative standard deviation values. TAC-Phen and TAC-Dpa could recognize Co2+ qualitatively, but could not detect Co2+ quantitatively. While TAC-Tpy, PAN-Tpy, PAN-Phen, and PAN-Dpa showed no metal ion selectivity. The experimental results were also rationalized by theoretical studies. A mixed ligand system can be used to produce a ratiometric absorption signal to avoid most ambiguities, such as the chemosensor environment and concentration, via self-calibration of two absorption bands. Structural insights derived from detection activities can provide valuable information for the design of new metal ion chemosensors by varying the type of organic ligands. Graphical abstracts The work represents a simple strategy for obtaining synthesis-free, inexpensive, and sensitivity-tunable chemosensors through mixing organic ligands of different sizes, substitutions, geometries, and connectivity to modulate the sensing behaviors.

Activation of Phox2b-Expressing Neurons in the Nucleus Tractus Solitarii Drives Breathing in Mice.

The nucleus tractus solitarii (NTS) is implicated in the control of breathing, but the neuronal phenotype and circuit mechanism involved in such a physiological function remain incompletely understood. This study focused on the respiratory role of paired-like homeobox 2b gene (Phox2b)-expressing NTS neurons and sought to determine whether selective stimulation of this set of neurons activates breathing in male mice. A Cre-dependent vector encoding a Gq-coupled human M3 muscarinic receptor (hM3Dq) was microinjected into the NTS of Phox2b-Cre transgenic mice. The hM3Dq-transduced neurons were pharmacologically activated in conscious mice while respiratory effects were measured by plethysmography. We demonstrate that chemogenetic stimulation of Phox2b-expressing NTS neurons significantly increased baseline minute volume via an increase in respiratory frequency rather than tidal volume. Chemogenetic stimulation also synergized with moderate CO2 stimulation to enhance pulmonary ventilatory response. Selective ablation of Phox2b-expressing NTS neurons notably attenuated a hypercapnic ventilatory response. Moreover, histological evidence revealed that stimulation of Phox2b-expressing NTS neurons increased neuronal activity of the preBötzinger complex. Finally, we presented the neuroanatomical evidence of direct projection of Phox2b-expressing NTS neurons to putative respiratory central pattern generator. Overall, these findings suggest that selective activation of Phox2b-expressing NTS neurons potentiates baseline pulmonary ventilation via an excitatory drive to respiratory central pattern generator and this group of neurons is also required for the hypercapnic ventilatory response.SIGNIFICANCE STATEMENT The nucleus tractus solitarii (NTS) has been implicated in the control of breathing. The paired-like homeobox 2b gene (Phox2b) is the disease-defining gene for congenital central hypoventilation syndrome and is restrictively present in brainstem nucleus, including the NTS. Using a chemogenetic approach, we demonstrate herein that selective stimulation of Phox2b-expressing NTS neurons vigorously potentiates baseline pulmonary ventilation via an excitatory drive to respiratory central pattern generator in rodents. Genetic ablation of these neurons attenuates the hypercapnic ventilatory response. We also suggest that a fraction of Phox2b-expressing neurons exhibit CO2 sensitivity and presumably function as central respiratory chemoreceptors. The methodology is expected to provide a future applicability to the patients with sleep-related hypoventilation or apnea.

High sensitivity of a keystone forage fish to elevated CO2 and temperature.

Sand lances of the genus Ammodytes are keystone forage fish in coastal ecosystems across the northern hemisphere. Because they directly support populations of higher trophic organisms such as whales, seabirds or tuna, the current lack of empirical data and, therefore, understanding about the climate sensitivity of sand lances represent a serious knowledge gap. Sand lances could be particularly susceptible to ocean warming and acidification because, in contrast to other tested fish species, they reproduce during boreal winter months, and their offspring develop slowly under relatively low and stable pCO2 conditions. Over the course of 2 years, we conducted factorial pCO2 × temperature exposure experiments on offspring of the northern sand lance Ammodytes dubius, a key forage species on the northwest Atlantic shelf. Wild, spawning-ripe adults were collected from Stellwagen Bank National Marine Sanctuary (Cape Cod, USA), and fertilized embryos were reared at three pCO2 conditions (400, 1000 and 2100 μatm) crossed with three temperatures (5, 7 and 10 ˚C). Exposure to future pCO2 conditions consistently resulted in severely reduced embryo survival. Sensitivity to elevated pCO2 was highest at 10 ˚C, resulting in up to an 89% reduction in hatching success between control and predicted end-of-century pCO2 conditions. Moreover, elevated pCO2 conditions delayed hatching, reduced remaining endogenous energy reserves at hatch and reduced embryonic growth. Our results suggest that the northern sand lance is exceptionally CO2-sensitive compared to other fish species. Whether other sand lance species with similar life history characteristics are equally CO2-sensitive is currently unknown. But the possibility is a conservation concern, because many boreal shelf ecosystems rely on sand lances and might therefore be more vulnerable to climate change than currently recognized. Our findings indicate that life history, spawning habitat, phenology and developmental rates mediate the divergent early life CO2 sensitivities among fish species.