Cooperation in public goods game does not require assortment and depends on population density.

The threshold public goods game is one of the best-known models of non-linear public goods dilemmas. Cooperators and defectors typically coexist in this game when the population is assumed to follow the so-called structured deme model. In this article, we develop a dynamical model of a general N-player game in which there is no deme structure: Individuals interact with randomly chosen neighbours and selection occurs between randomly chosen pairs of individuals. We show that in the deterministic limit, the dynamics in this model leads to the same replicator dynamics as in the structured deme model, i.e., coexistence of cooperators and defectors is typical in threshold public goods game even when the population is completely well mixed. We extend the model to study the effect of density dependence and density fluctuation on the dynamics. We show analytically and numerically that decreasing population density increases the equilibrium frequency of cooperators till the fixation of this strategy, but below a critical density cooperators abruptly disappear from the population. Our numerical investigations show that weak density fluctuations enhance cooperation, while strong fluctuations suppress it.

Synthesis of gem-Difluorinated 2,3-Dihydrobenzofurans Using Freon-22 via [4 + 1] Annulation of Difluorocarbene and Antitumor Activity Evaluation.

As an inexpensive industrial chemical, chlorodifluoromethane (Freon-22), despite its relatively low reactivity, can serve as a practical CF2 source for the construction of gem-difluorinated ring structures. Here, we develop a protocol for the efficient assembly of valuable fluorinated 2,3-dihydrobenzofurans from the [4 + 1] annulation in good yields under basic conditions. The reliable practicability and scalability of the process have also been demonstrated by preparation at the multigram scale, late-stage modifications of pharmaceutical molecules, and potential antitumor potency.

[Two cases of acute freon poisoning].

Freon is widely used in daily life, which is usually absorbed through the respiratory tract and causes clinical manifestations mainly in the cardiovascular system and neurological damage. Now, we analyze the clinical data, diagnosis, treatment and prognosis of two cases of freon poisoning in Affiliated Dongyang People's Hospital of Wenzhou Medical University to improve the clinicians' understanding of freon poisoning and to avoid missed diagnosis and misdiagnosis.

Inverse Modeling Revealed Reversed Trends in HCFC-141b Emissions for China during 2018-2020.

Having the highest ozone-depleting potential among hydrochlorofluorocarbons (HCFCs), the production and consumption of HCFC-141b (1,1-dichloro-1-fluoroethane, CH3CCl2F) are controlled by the Montreal Protocol. A renewed rise in global HCFC-141b emissions was found during 2017-2020; however, the latest changes in emissions across China are unclear for this period. This study used the FLEXible PARTicle dispersion model and the Bayesian framework to quantify HCFC-141b emissions based on atmospheric measurements from more sites across China than those used in previous studies. Results show that the estimated HCFC-141b emissions during 2018-2020 were on average 19.4 (17.3-21.6) Gg year-1, which was 3.9 (0.9-7.0) Gg year-1 higher than those in 2017 (15.5 [13.4-17.6] Gg year-1), showing a renewed rise. The proportion of global emissions that could not be exactly traced in 2020 was reduced from about 70% reported in previous studies to 46% herein. This study reconciled the global emission rise of 3.0 ± 1.2 Gg year-1 (emissions in 2020 - emissions in 2017): China's HCFC-141b emissions changed by 4.3 ± 4.5 Gg year-1, and the combined emissions from North Korea, South Korea, western Japan, Australia, northwestern Europe, and the United States changed by -2.2 ± 2.6 Gg year-1, while those from other countries/regions changed by 0.9 ± 5.3 Gg year-1.

The wide presence of fluorinated compounds in common chemical products and the environment: a review.

The C-F bonds, due to their many unique features, have been incorporated into numerous compounds in countless products and applications. These fluorinated compounds eventually are disposed of and released into the environment through different pathways. In this review, we analyzed the occurrence of these fluorinated compounds in seven types of products (i.e., refrigerants/propellants, aqueous film-forming foam, cosmetics, food packaging, agrochemicals, pharmaceuticals, coating materials) and discussed their fate in the environment. This is followed by describing the quantity of fluorinated compounds from each source based on available data. Total on- and off-site disposal or other releases of 536 fluorinated compounds in 2021 were analyzed using the data sourced from the U.S. EPA Toxics Release Inventory (TRI). Among the chemicals examined, chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) were the primary contributors in terms of total mass. Upon examining the seven sources of fluorinated compounds, it became evident that additional contributors are also responsible for the presence of organofluorine compounds in the environment. Although various toxic degradation products of fluorinated compounds could form in the environment, trifluoroacetic acid (TFA) was specifically highlighted in this review given the fact that it is a common dead-end degradation product of > 1 million chemicals. This paper ended with a discussion of several questions raised from this study. The path forward was elaborated as well for the purpose of protecting the environment and human health.

Hydrodehalogenation of Trichlorofluoromethane over Biogenic Palladium Nanoparticles in Ambient Conditions.

Among a number of persistent chlorofluorocarbons (CFCs, or freons), the emissions of trichlorofluoromethane (CFCl3, CFC-11) have been increasing since 2002. Zero-valent-Pd (Pd0) catalysts are known to hydrodehalogenate CFCs; however, most studies rely on cost-inefficient and eco-unfriendly chemical synthesis of Pd0NPs and harsh reaction conditions. In this study, we synthesized Pd0 nanoparticles (Pd0NPs) using D. vulgaris biomass as the support and evaluated hydrodehalogenation of CFC-11 catalyzed by the biogenic Pd0NPs. The presence of D. vulgaris biomass stabilized and dispersed 3-6 nm Pd0NPs that were highly active. We documented, for the first time, Pd0-catalyzed simultaneous hydrodechlorination and hydrodefluorination of CFC-11 at ambient conditions (room temperature and 1 atm). More than 70% CFC-11 removal was achieved within 15 h with a catalytic activity of 1.5 L/g-Pd/h, dechlorination was 50%, defluorination was 41%, and selectivity to fully dehalogenated methane was >30%. The reaction pathway had a mixture of parallel and sequential hydrodehalogenation. In particular, hydrodefluorination was favored by higher H2 availability and Pd0:CFC-11 ratio. This study offers a promising strategy for efficient and sustainable treatment of freon-contaminated water.

Difluoromethylation of Unactivated Alkenes Using Freon-22 through Tertiary Amine-Borane-Triggered Halogen Atom Transfer.

The application of abundant and inexpensive fluorine feedstock sources to synthesize fluorinated compounds is an appealing yet underexplored strategy. Here, we report a photocatalytic radical hydrodifluoromethylation of unactivated alkenes with an inexpensive industrial chemical, chlorodifluoromethane (ClCF2H, Freon-22). This protocol is realized by merging tertiary amine-ligated boryl radical-induced halogen atom transfer (XAT) with organophotoredox catalysis under blue light irradiation. A broad scope of readily accessible alkenes featuring a variety of functional groups and drug and natural product moieties could be selectively difluoromethylated with good efficiency in a metal-free manner. Combined experimental and computational studies suggest that the key XAT process of ClCF2H is both thermodynamically and kinetically favored over the hydrogen atom transfer pathway owing to the formation of a strong boron-chlorine (B-Cl) bond and the low-lying antibonding orbital of the carbon-chlorine (C-Cl) bond.

Electrochemical collective synthesis of labeled pyrroloindoline alkaloids with Freon-type methanes as functional C1 synthons.

Utilization of Freon-type methanes as functional one-carbon synthons in the synthesis of various deuterated indoline alkaloids was demonstrated here. A series of halomethyl radicals were generated from electro-reductive C-X cleavage of Freon-type methanes and captured efficiently by acrylamides to provide various halogenated oxindoles via radical cyclization. This reaction features good functional group tolerance, and deuterium and fluorine atoms could be introduced facilely from Freon-type methanes. Further transformation of halogenated oxindoles enabled the synthesis of many (labeled) bioactive drug molecules and skeletons, such as deuterated (±)-physostigmine, deuterated (±)-esermethole and deuterated (±)-lansai B.

A case report of recreational use of inhaled Freon leading to acute hypoxemic respiratory failure salvaged by veno-venous extracorporeal membrane oxygenation.

BACKGROUND: Freon™ is a halogenated hydrocarbon often used as a refrigerant. When inhaled recreationally, it has the desired effects of euphoria and intoxication. Toxic effects include cardiovascular and neurologic insults such as arrhythmias and seizures, and less well-described toxicities include airway and lung injury. The treatment in general is primarily supportive. CLINICAL FEATURES: We present the case of a 42-yr-old previously healthy male who developed acute bronchiolitis and pneumonitis following inhalation of Freon leading to severe respiratory failure. He was supported by veno-venous extracorporeal membrane oxygenation and managed with high-dose corticosteroids. CONCLUSION: To our knowledge, this is the first case report of an inhaled Freon exposure resulting in acute lung injury refractory to conventional therapy that was salvaged by vv-ECMO as a bridge towards a full recovery.

RéSUMé: CONTEXTE: Le Fréon™ est un hydrocarbure halogéné souvent utilisé comme réfrigérant. Lorsqu'il est inhalé à des fins récréatives, il a les effets souhaités d'euphorie et d'intoxication. Les effets toxiques comprennent les lésions cardiovasculaires et neurologiques telles que les arythmies et les convulsions, et les toxicités moins bien décrites comprennent les lésions des voies aériennes et des poumons. En général, le traitement est principalement un traitement de soutien. CARACTéRISTIQUES CLINIQUES: Nous présentons le cas d'un homme de 42 ans auparavant en bonne santé qui a développé une bronchiolite et une pneumonite aiguës après inhalation de Fréon, entraînant une insuffisance respiratoire sévère. Il a été supplémenté par oxygénation par membrane extracorporelle veino-veineuse et pris en charge avec des corticostéroïdes à forte dose. CONCLUSION: À notre connaissance, il s'agit de la première présentation de cas d'exposition au Fréon inhalé entraînant une lésion pulmonaire aiguë réfractaire au traitement conventionnel et pour laquelle un sauvetage par ECMO-VV a favorisé un rétablissement complet.

Using gridCoal to assess whether standard population genetic theory holds in the presence of spatio-temporal heterogeneity in population size.

Spatially explicit population genetic models have long been developed, yet have rarely been used to test hypotheses about the spatial distribution of genetic diversity or the genetic divergence between populations. Here, we use spatially explicit coalescence simulations to explore the properties of the island and the two-dimensional stepping stone models under a wide range of scenarios with spatio-temporal variation in deme size. We avoid the simulation of genetic data, using the fact that under the studied models, summary statistics of genetic diversity and divergence can be approximated from coalescence times. We perform the simulations using gridCoal, a flexible spatial wrapper for the software msprime (Kelleher et al., 2016, Theoretical Population Biology, 95, 13) developed herein. In gridCoal, deme sizes can change arbitrarily across space and time, as well as migration rates between individual demes. We identify different factors that can cause a deviation from theoretical expectations, such as the simulation time in comparison to the effective deme size and the spatio-temporal autocorrelation across the grid. Our results highlight that FST , a measure of the strength of population structure, principally depends on recent demography, which makes it robust to temporal variation in deme size. In contrast, the amount of genetic diversity is dependent on the distant past when Ne is large, therefore longer run times are needed to estimate Ne than FST . Finally, we illustrate the use of gridCoal on a real-world example, the range expansion of silver fir (Abies alba Mill.) since the last glacial maximum, using different degrees of spatio-temporal variation in deme size.

Estimate of hydrochlorofluorocarbon emissions during 2011-2018 in the Yangtze River Delta, China.

Hydrochlorofluorocarbons (HCFCs) are used as temporary substitutes for chlorofluorocarbons and other ozone-depleting substances because they have reduced ozone depletion and global warming potentials. The consumption and production of HCFCs are regulated via the Montreal Protocol and its amendments till 2013, with a complete phase-out being scheduled by 2030 for Article 5 parties (developing countries). To better understand the characteristics and emissions of HCFCs in the Yangtze River Delta (YRD), which is the largest metropolitan area in China, weekly flask samples were collected at the Lin'an regional background station located in the YRD from 2011 to 2018 and measured for four HCFCs (HCFC-22, HCFC-141b, HCFC-142b, and HCFC-124). The HCFC-132b and HCFC-133a measurements began in 2018. The ambient mixing ratios of the HCFCs exhibited higher concentrations and larger variabilities than those at the Shangri-la regional background station at similar latitudes in southwest China. The HCFC emissions in the YRD were estimated based on the tracer ratio method using CO and HFC-134a as tracers, and were comparable within the uncertainties. Our results are generally consistent with previous estimates obtained using top-down approaches. HCFC-22 and HCFC-141b contributed 52% ± 23% and 41% ± 24% of the total ODP-weighted (CFC-11-equivalent) HCFC emissions from the YRD, respectively, whereas HCFC-22 contributed the most (83% ± 36%) to the total CO2-equivalent HCFC emissions from the YRD. The cumulative ODP-weighted and CO2-equivalent emissions of HCFCs from the YRD accounted for 25% ± 15% and 20% ± 11% of the national corresponding totals, respectively, for 2011-2017. The HCFC-141b emissions from the YRD contributed approximately half of the total Chinese emissions. HCFC-133a emissions in the YRD accounted for approximately one-fifth of the global total in 2018. Thus, the YRD is an important contributor of HCFC emissions on national and global scales.

Age distribution of Antarctic Bottom Water off Cape Darnley, East Antarctica, estimated using chlorofluorocarbon and sulfur hexafluoride.

Chlorofluorocarbon (CFC) and sulfur hexafluoride (SF6) were used to investigate the timescale of Antarctic Bottom Water (AABW) that spreads off Cape Darnley (CD) in East Antarctica. The age of the AABW was estimated based on the observed SF6/CFC-12 ratio while taking into account tracer dilution by Lower Circumpolar Deep Water. Along the western canyons off CD and the ~ 3000 to 3500 m isobaths, the bottom water age was < 5 years, reflecting the spread of newly formed CD Bottom Water. Higher ages of ~ 8 years obtained for areas east of CD and > 20 years in the northwestern offshore region indicate inflows of AABW through the Princess Elizabeth Trough and Weddell Sea Deep Water, respectively. This study determined the age distribution in the region off CD, where three different types of AABW spread.

Narrowing feedstock exemptions under the Montreal Protocol has multiple environmental benefits.

The Montreal Protocol on Substances that Deplete the Ozone Layer (Montreal Protocol) can be further strengthened to control ozone-depleting substances and hydrofluorocarbons used as feedstocks to provide additional protection of the stratospheric ozone layer and the climate system while also mitigating plastics pollution. The feedstock exemptions were premised on the assumption that feedstocks presented an insignificant threat to the environment; experience has shown that this is incorrect. Through its adjustment procedures, the Montreal Protocol can narrow the scope of feedstock exemptions to reduce inadvertent and unauthorized emissions while continuing to exempt production of feedstocks for time-limited, essential uses. This upstream approach can be an effective and efficient complement to other efforts to reduce plastic pollution. Existing mechanisms in the Montreal Protocol such as the Assessment Panels and national implementation strategies can guide the choice of environmentally superior substitutes for feedstock-derived plastics. This paper provides a framework for policy makers, industries, and civil society to consider how stronger actions under the Montreal Protocol can complement other chemical and environmental treaties.

A review of bottom-up and top-down emission estimates of hydrofluorocarbons (HFCs) in different parts of the world.

Hydrofluorocarbons (HFCs) are widespread alternatives for the ozone-depleting substances chlorofluorocarbons and hydrochlorofluorocarbons. They are used mainly as refrigerants or as foam-blowing agents. HFCs do not deplete the ozone layer, but they are very potent greenhouse gases, already contributing to global warming. Since 2019 HFCs are regulated under the Kigali Amendment to the Montreal Protocol, which demands reliable emission estimates to monitor the phase-down. Quantification of emissions is performed with two methods: bottom-up from product inventories or data on chemical sales; or top-down, inferred from atmospheric measurements by inverse modelling or interspecies correlation. Here, we review and compare the two methods and give an overview of HFC emissions from different parts of the world. Emission estimates reported by the different methods vary considerably. HFC emissions of developed countries (Annex I) are reported to the United Nations Framework Convention on Climate Change. These bottom-up estimates add up to only half of global emissions estimated from atmospheric data. Several studies with regional top-down estimates have shown that this gap is not owed to large-scale underreporting of emissions from developed countries, but mostly due to emissions from developing countries (non-Annex I). China accounts for a large fraction of the emissions causing the gap, but not entirely. Bottom-up and top-down estimations of emissions from other developing countries that could identify other large emitters are largely unavailable. Especially South America, West-, Central- and East-Africa, India, the Arabian Peninsula and Northern Australia are not well covered by measurement stations that could provide atmospheric data for top-down estimates.

The atmospheric concentrations and emissions of major halocarbons in China during 2009-2019.

Due to the characteristics of ozone-depleting and high global warming potential, chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs) have been restricted by the Montreal Protocol and its amendments over the world. Considering that China is one of the main contributors to the emission of halocarbons, a long-term atmospheric observation on major substances including CFC-11 (CCl3F), CFC-12 (CCl2F2), HCFC-22 (CHClF2), HCFC-141b (CH3CCl2F), HCFC-142b (CH3CClF2) and HFC-134a (CH2FCF3) was conducted in five cities (Beijing, Hangzhou, Guangzhou, Lanzhou and Chengdu) of China during 2009-2019. The atmospheric concentrations of CFC-11, CFC-12, HCFC-141b and HCFC-142b all showed declining trends on the whole while those of HCFC-22 and HFC-134a were opposite. A paired sample t-test showed that the ambient mixing ratios of HCFC-22 and HFC-134a in cities were 41.9% and 25.7% higher on average than those in suburban areas, respectively, while the other substances did not show significant regional differences. The annual emissions of halocarbons were calculated using an interspecies correlation method and the results were generally consistent with the published estimates. Discrepancies between bottom-up inventories and the estimates in this study for CFCs emissions were found. Among the most consumed ozone depleting substances (ODSs) in China, CFCs accounted for 75.1% of the ozone depletion potential (ODP)-weighted emissions while HCFCs contributed a larger proportion (58.6%) of CO2-equivalent emissions in 2019. China's emissions of HCFC-141b and HCFC-142b contributed the most to the global emission (17.8%-48.0%). The elimination of HCFCs in China will have a crucial impact on the HCFCs phase-out in the world.

Tunable Mechanical and Electrical Properties of Coaxial Electrospun Composite Nanofibers of P(VDF-TrFE) and P(VDF-TrFE-CTFE).

The coaxial core/shell composite electrospun nanofibers consisting of relaxor ferroelectric P(VDF-TrFE-CTFE) and ferroelectric P(VDF-TrFE) polymers are successfully tailored towards superior structural, mechanical, and electrical properties over the individual polymers. The core/shell-TrFE/CTFE membrane discloses a more prominent mechanical anisotropy between the revolving direction (RD) and cross direction (CD) associated with a higher tensile modulus of 26.9 MPa and good strength-ductility balance, beneficial from a better degree of nanofiber alignment, the increased density, and C-F bonding. The interfacial coupling between the terpolymer P(VDF-TrFE-CTFE) and copolymer P(VDF-TrFE) is responsible for comparable full-frequency dielectric responses between the core/shell-TrFE/CTFE and pristine terpolymer. Moreover, an impressive piezoelectric coefficient up to 50.5 pm/V is achieved in the core/shell-TrFE/CTFE composite structure. Our findings corroborate the promising approach of coaxial electrospinning in efficiently tuning mechanical and electrical performances of the electrospun core/shell composite nanofiber membranes-based electroactive polymers (EAPs) actuators as artificial muscle implants.

On the effects of the ocean on atmospheric CFC-11 lifetimes and emissions.

The ocean is a reservoir for CFC-11, a major ozone-depleting chemical. Anthropogenic production of CFC-11 dramatically decreased in the 1990s under the Montreal Protocol, which stipulated a global phase out of production by 2010. However, studies raise questions about current overall emission levels and indicate unexpected increases of CFC-11 emissions of about 10 Gg ⋅ yr-1 after 2013 (based upon measured atmospheric concentrations and an assumed atmospheric lifetime). These findings heighten the need to understand processes that could affect the CFC-11 lifetime, including ocean fluxes. We evaluate how ocean uptake and release through 2300 affects CFC-11 lifetimes, emission estimates, and the long-term return of CFC-11 from the ocean reservoir. We show that ocean uptake yields a shorter total lifetime and larger inferred emission of atmospheric CFC-11 from 1930 to 2075 compared to estimates using only atmospheric processes. Ocean flux changes over time result in small but not completely negligible effects on the calculated unexpected emissions change (decreasing it by 0.4 ± 0.3 Gg ⋅ yr-1). Moreover, it is expected that the ocean will eventually become a source of CFC-11, increasing its total lifetime thereafter. Ocean outgassing should produce detectable increases in global atmospheric CFC-11 abundances by the mid-2100s, with emission of around 0.5 Gg ⋅ yr-1; this should not be confused with illicit production at that time. An illustrative model projection suggests that climate change is expected to make the ocean a weaker reservoir for CFC-11, advancing the detectable change in the global atmospheric mixing ratio by about 5 yr.

Evaluation of fluorine-19 magnetic resonance imaging of the lungs using octafluorocyclobutane in a rat model.

PURPOSE: To test octafluorocyclobutane (OFCB) as an inhalation contrast agent for fluorine-19 MRI of the lung, and to compare the image quality of OFCB scans with perfluoropropane (PFP) scans THEORY AND METHODS: After normalizing for the number of signal averages, a theoretical comparison between the OFCB signal-to-noise ratio (SNR) and PFP SNR predicted the average SNR advantage of 90% using OFCB during gradient echo imaging. The OFCB relaxometry was conducted using single-voxel spectroscopy and spin-echo imaging. A comparison of OFCB and PFP SNRs was performed in vitro and in vivo. Five healthy Sprague-Dawley rats were imaged during single breath-hold and continuous breathing using a Philips Achieva 3.0T MRI scanner (Philips, Andover, MA). The scan time was constant for both gases. Statistical comparison between PFP and OFCB scans was conducted using a paired t test and by calculating the Bayes factor. RESULTS: Spin-lattice (T1 ) and effective spin-spin ( T2∗ ) relaxation time constants of the pure OFCB gas were determined as 28.5 ± 1.2 ms and 10.5 ± 1.8 ms, respectively. Mixing with 21% of oxygen decreased T1 by 30% and T2∗ by 20%. The OFCB in vivo images showed 73% higher normalized SNR on average compared with images acquired using PFP. The statistical significance was shown by both paired t test and calculated Bayes factors. The experimental results agree with theoretical calculations within the error of the relaxation parameter measurements. CONCLUSION: The quality of the lung images acquired using OFCB was significantly better compared with PFP scans. The OFCB images had higher a SNR and were artifact-free.

Effect of carrier solvent in 1,2-indanedione formulation on the development of fingermarks on porous substrates.

As an important technique for the detection of fingermarks on porous surfaces, 1,2-indanedione is widely used due to its excellent detection performance. In order to optimize the effectiveness of 1,2-indanedione, several institutions have modified the original formulation. In this study, four different 1,2-indanedione formulations were used to treat fingermarks deposited on different porous substrates to determine the most suitable formulation and whether Solstice-PF can be an alternative carrier solvent for the currently used HFE7100. It was found that the Solstice-PF-based formulation performed similarly to the HFE7100-based formulation on copy paper, but when treating fingermarks deposited on brown paper and newspaper, Solstice-PF was superior to HFE7100 by developing up to 10% more marks graded 3 and 4 regardless of the ageing period. The results confirm that Solstice-PF can be used as an alternative carrier solvent for 1,2-indanedione formulations with good detection rates and lower costs.