Resolving Atmospheric Oxygenated Organic Molecules in Urban Beijing Using Online Ultrahigh-Resolution Chemical Ionization Mass Spectrometry.

Gaseous oxygenated organic molecules (OOMs) are crucial precursors of atmospheric organic aerosols. OOMs in urban atmospheres have complex compositions, posing challenges to understanding their formation, evolution, and influences. In this study, we identify 2403 atmospheric gaseous OOMs in urban Beijing using online nitrate-based chemical ionization Orbitrap mass spectrometry based on one-year atmospheric measurements. We find that OOMs in urban atmospheres can be identified with higher accuracy and wider coverage, compared to previously used online mass spectrometry. With optimized OOM resolving capabilities, previous knowledge of OOMs in urban atmospheres can be expanded. First, clear homologous and oxygen-addition characteristics of the OOMs are revealed. Second, OOMs with lower concentrations or higher masses are identified and characterized with high confidence, e.g., OOMs with masses above 350 Da. In particular, dimers of OOMs (e.g., C20H32O8-15N2), crucial species for organic nucleation, are identified. During four seasons, nitrogen-containing OOMs dominate the total concentration of OOMs, and OOMs are mainly from aromatic and aliphatic oxidation. Additionally, radicals with similar composition as OOMs, intermediates for OOM formation, are identified with clear diurnal variation, e.g., CnH2n-5O6 radicals (n = 8-10) and CmH2m-4NO9 radicals (m = 9-10), peak during the daytime and nighttime, respectively, previously having scarce measurement evidence in urban atmospheres.

Pollution gradients shape microbial communities associated with ae. albopictus larval habitats in urban community gardens.

The Asian tiger mosquito Aedes albopictus is well adapted to urban environments and takes advantage of the artificial containers that proliferate in anthropized landscapes. Little is known about the physicochemical, pollutant and microbiota compositions of Ae. albopictus-colonized aquatic habitats and whether these properties differ with noncolonized habitats. We specifically addressed this question in French community gardens by investigating whether pollution gradients (characterized either by water physicochemical properties combined with pollution variables or by the presence of organic molecules in water) influence water microbial composition and then the presence/absence of Ae. albopictus mosquitoes. Interestingly, we showed that the physicochemical and microbial compositions of noncolonized and colonized waters did not significantly differ, with the exception of N2O and CH4 concentrations, which were higher in noncolonized water samples. Moreover, the microbial composition of larval habitats covaried differentially along the pollution gradients according to colonization status. This study opens new avenues on the impact of pollution on mosquito habitats in urban areas and raises questions on the influence of biotic and abiotic interactions on adult life history traits and their ability to transmit pathogens to humans.

The Pivotal Role of Heavy Terpenes and Anthropogenic Interactions in New Particle Formation on the Southeastern Qinghai-Tibet Plateau.

Aerosol particles originating from the Qinghai-Tibet Plateau (QTP) readily reach the free troposphere, potentially affecting global radiation and climate. Although new particle formation (NPF) is frequently observed at such high altitudes, its precursors and their underlying chemistry remain poorly understood. This study presents direct observational evidence of anthropogenic influences on biogenic NPF on the southeastern QTP, near the Himalayas. The mean particle nucleation rate (J1.7) is 2.6 cm-3 s-1, exceeding the kinetic limit of sulfuric acid (SA) nucleation (mean SA: 2.4 × 105 cm-3). NPF is predominantly driven by highly oxygenated organic molecules (HOMs), possibly facilitated by low SA levels. We identified 1538 ultralow-volatility HOMs driving particle nucleation and 764 extremely low-volatility HOMs powering initial particle growth, with mean total concentrations of 1.5 × 106 and 3.7 × 106 cm-3, respectively. These HOMs are formed by atmospheric oxidation of biogenic precursors, unexpectedly including sesquiterpenes and diterpenes alongside the commonly recognized monoterpenes. Counterintuitively, over half of HOMs are organic nitrates, mainly produced by interacting with anthropogenic NOx via RO2+NO terminations or NO3-initiated oxidations. These findings advance our understanding of NPF mechanisms in this climate-sensitive region and underscore the importance of heavy terpene and NOx-influenced chemistry in assessing anthropogenic-biogenic interactions with climate feedbacks.

Modulation of Electrostatic Potential in 2D Crystal Engineered by an Array of Alternating Polar Molecules.

The moiré potential in rotationally misfit two-dimensional (2D) heterostructures has been used to build artificial exciton and electron lattices, which have become platforms for realizing exotic electronic phases. Here, we demonstrate a different approach to create a superlattice potential in 2D crystals by using the near field of an array of polar molecules. A bilayer of titanyl phthalocyanine (TiOPc), consisting of alternating out-of-plane dipoles, is deposited on monolayer MoS2. Time-resolved two-photon photoemission spectroscopy reveals a pair of interlayer exciton states with an energy difference of ∼0.1 eV, which is consistent with the electrostatic potential modulation induced by the TiOPc bilayer as determined by density functional theory calculations. Because the symmetry and the period of this potential superlattice can be changed readily by using molecules of different shapes and sizes, molecule/2D heterostructures can be promising platforms for designing artificial exciton and electron lattices.

Active control of polariton-enabled long-range energy transfer.

Optical control is achieved on the excited state energy transfer between spatially separated donor and acceptor molecules, both coupled to the same optical mode of a cavity. The energy transfer occurs through the formed hybrid polaritons and can be switched on and off by means of ultraviolet and visible light. The control mechanism relies on a photochromic component used as donor, whose absorption and emission properties can be varied reversibly through light irradiation, whereas in-cavity hybridization with acceptors through polariton states enables a 6-fold enhancement of acceptor/donor contribution to the emission intensity with respect to a reference multilayer. These results pave the way for synthesizing effective gating systems for the transport of energy by light, relevant for light-harvesting and light-emitting devices, and for photovoltaic cells.

The Hunt for Chemical Dark Matter across a River-to-Ocean Continuum.

Thousands of mass peaks emerge during molecular characterization of natural dissolved organic matter (DOM) using ultrahigh-resolution mass spectrometry. While mass peaks assigned to certain molecular formulas have been extensively studied, the uncharacterized mass peaks that represent a significant fraction of organic matter and convey biogenic elements and energy have been previously ignored. In this study, we introduce the term dark DOM (DDOM) for unassigned mass peaks and have explored its characteristics and environmental behaviors using a data set of 38 DOM extracts covering the Yangtze River-to-ocean continuum. We identified a total of 9141 DDOM molecules, which exhibited higher molecular weight and greater diversity than the DOM subset with assigned DOM formulas. Although DDOM contributed a smaller fraction of relative abundance, it significantly impacted the molecular weight and molecular composition of bulk DOM. A portion of DDOM with higher molecular weight was found to increase molecular abundance across the river-to-ocean continuum. These compounds could contain halogenated organic molecules and might have a high potential to contribute to the refractory organic carbon pool. With this study, we underline the contribution of dark matter to the total DOM pool and emphasize that more DDOM research is needed to understand its contribution to global biogeochemical cycles and carbon sequestration.

How the addition of atomic hydrogen to a multiple bond can be catalyzed by water molecules.

Observational data show complex organic molecules in the interstellar medium (ISM). Hydrogenation of small unsaturated carbon double bond could be one way for molecular complexification. It is important to understand how such reactivity occurs in the very cold and low-pressure ISM. Yet, there is water ice in the ISM, either as grain or as mantle around grains. Therefore, the addition of atomic hydrogen on double-bonded carbon in a series of seven molecules have been studied and it was found that water catalyzes this reaction. The origin of the catalysis is a weak charge transfer between the π MO of the unsaturated molecule and H atom, allowing a stabilizing interaction with H2O. This mechanism is rationalized using the non-covalent interaction and the quantum theory of atoms in molecules approaches.

Fostering a Holistic Understanding of the Full Volatility Spectrum of Organic Compounds from Benzene Series Precursors through Mechanistic Modeling.

A comprehensive understanding of the full volatility spectrum of organic oxidation products from the benzene series precursors is important to quantify the air quality and climate effects of secondary organic aerosol (SOA) and new particle formation (NPF). However, current models fail to capture the full volatility spectrum due to the absence of important reaction pathways. Here, we develop a novel unified model framework, the integrated two-dimensional volatility basis set (I2D-VBS), to simulate the full volatility spectrum of products from benzene series precursors by simultaneously representing first-generational oxidation, multigenerational aging, autoxidation, dimerization, nitrate formation, etc. The model successfully reproduces the volatility and O/C distributions of oxygenated organic molecules (OOMs) as well as the concentrations and the O/C of SOA over wide-ranging experimental conditions. In typical urban environments, autoxidation and multigenerational oxidation are the two main pathways for the formation of OOMs and SOA with similar contributions, but autoxidation contributes more to low-volatility products. NOx can reduce about two-thirds of OOMs and SOA, and most of the extremely low-volatility products compared to clean conditions, by suppressing dimerization and autoxidation. The I2D-VBS facilitates a holistic understanding of full volatility product formation, which helps fill the large gap in the predictions of organic NPF, particle growth, and SOA formation.

Defects and Defect Passivation in Perovskite Solar Cells.

Perovskite solar cells have made significant strides in recent years. However, there are still challenges in terms of photoelectric conversion efficiency and long-term stability associated with perovskite solar cells. The presence of defects in perovskite materials is one of the important influencing factors leading to subpar film quality. Adopting additives to passivate defects within perovskite materials is an effective approach. Therefore, we first discuss the types of defects that occur in perovskite materials and the mechanisms of their effect on performance. Then, several types of additives used in perovskite solar cells are discussed, including ionic compounds, organic molecules, polymers, etc. This review provides guidance for the future development of more sustainable and effective additives to improve the performance of solar cells.

Temperature effects and molecular insights towards the optimization of polyvinyl alcohol as adsorbent of organic pollutants from aqueous solution.

One of the easier methods of wastewater treatment is adsorption due to its simplicity in implementation, environmental friendliness, and economic feasibility. Polyvinyl alcohol (PVA) looks promising as an adsorbent due to its biocompatible, non-toxic, water-soluble and eco-friendly nature. The investigation of PVA for its potential in the adsorption of pollutants has been reported in many studies but the mechanistic understanding of the adsorption is poor. The present study used a theoretical approach through density functional theory and Monte Carlo with molecular dynamics simulations to investigate the adsorption mechanism behaviors of model organic molecules (bromothymol blue (BTB), methylene blue (MB), metronidazole (MNZ) and tetracycline (TC)) on PVA surface. The quantum chemical calculations result showed that with the increase in PVA chains (2, 4, 8, 16, and 32 units), the zero-point energy decreases (from -308.79 to -4922.93 kcal/mol) while the dipole moment increases (from 4.37 to 87.52 Debye). Temperature effect on the PVA chain structures showed the same trends for all the chain units and with the increase in temperature (50-600 K), there are no appreciable changes in zero-point energy, enthalpy energy increases while Gibbs free energy decreases. Considering PVA-pollutant complexes, the effects of temperature on the structures showed that there are no appreciable changes in the zero-point energy, Gibbs free and thermal energies increase with an increase in temperature while the kinetic rate of reactions decreases with an increase in temperature. The enthalpy of the reaction showed different trends with antibiotic and dye complexes. In all the thermodynamic properties investigated and the rate of reaction, the order of affinity of the pollutants with PVA followed TC > MNZ > MB > BTB. Monte Carlo simulation was used to investigate the adsorption behavior of the pollutants on the surface of PVA. The negative adsorption energies (-366.56 to -2266.81 kcal/mol) in terms of affinity towards the pollutants on the surface of PVA followed the sequence TC > MNZ > BTB > MB and the molecular dynamic simulation results followed the same order. The obtained results give valuable insights into the mechanism and performance of PVA as an adsorbent. Most of these computational observations are in good agreement with the available experimental results.

Undecanoic Acid and L-Phenylalanine in Vermiculite: Detection, Characterization, and UV Degradation Studies for Biosignature Identification on Mars.

Solar radiation that arrives on the surface of Mars interacts with organic molecules present in the soil. The radiation can degrade or transform the organic matter and make the search for biosignatures on the planet's surface difficult. Therefore, samples to be analyzed by instruments on board Mars probes for molecular content should be selectively chosen to have the highest organic preservation content. To support the identification of organic molecules on Mars, the behavior under UV irradiation of two organic compounds, undecanoic acid and L-phenylalanine, in the presence of vermiculite and two chloride salts, NaCl and MgCl, was studied. The degradation of the molecule's bands was monitored through IR spectroscopy. Our results show that, while vermiculite acts as a photoprotective mineral with L-phenylalanine, it catalyzes the photodegradation of undecanoic acid molecules. On the other hand, both chloride salts studied decreased the degradation of both organic species acting as photoprotectors. While these results do not allow us to conclude on the preservation capabilities of vermiculite, they show that places where chloride salts are present could be good candidates for in situ analytic experiments on Mars due to their organic preservation capacity under UV radiation.

High-Performance Room Temperature Ammonia Sensors Based on Pure Organic Molecules Featuring B-N Covalent Bond.

Exploring organic semiconductor gas sensors with high sensitivity and selectivity is crucial for the development of sensor technology. Herein, for the first time, a promising chemiresistive organic polymer P-BNT based on a novel π-conjugated triarylboron building block is reported, showcasing an excellent responsivity over 30 000 (Ra/Rg) against 40 ppm of NH3, which is ≈3300 times higher than that of its B-N organic small molecule BN-H. More importantly, a molecular induction strategy to weaken the bond dissociation energy between polymer and NH3 caused by strong acid-base interaction is further executed to optimize the response and recovery time. As a result, the BN-H/P-BNT system with rapid response and recovery times can still exhibit a high responsivity of 718, which is among the highest reported NH3 chemiresistive sensors. Supported by in situ FTIR spectroscopy and theoretical calculations, it is revealed that the N-H fractions in BN-H small molecule promoted the charge distribution on phenyl groups, which increases charge delocalization and is more conducive to gas adsorption in such molecular systems. Notably, these distinctive small molecules also promoted charge transfer and enhanced electron concentration of the P-BNT sensing polymer, thus achieving superior B-N-containing organic molecules with excellent sensing performance.

Advancing material property prediction: using physics-informed machine learning models for viscosity.

In materials science, accurately computing properties like viscosity, melting point, and glass transition temperatures solely through physics-based models is challenging. Data-driven machine learning (ML) also poses challenges in constructing ML models, especially in the material science domain where data is limited. To address this, we integrate physics-informed descriptors from molecular dynamics (MD) simulations to enhance the accuracy and interpretability of ML models. Our current study focuses on accurately predicting viscosity in liquid systems using MD descriptors. In this work, we curated a comprehensive dataset of over 4000 small organic molecules' viscosities from scientific literature, publications, and online databases. This dataset enabled us to develop quantitative structure-property relationships (QSPR) consisting of descriptor-based and graph neural network models to predict temperature-dependent viscosities for a wide range of viscosities. The QSPR models reveal that including MD descriptors improves the prediction of experimental viscosities, particularly at the small data set scale of fewer than a thousand data points. Furthermore, feature importance tools reveal that intermolecular interactions captured by MD descriptors are most important for viscosity predictions. Finally, the QSPR models can accurately capture the inverse relationship between viscosity and temperature for six battery-relevant solvents, some of which were not included in the original data set. Our research highlights the effectiveness of incorporating MD descriptors into QSPR models, which leads to improved accuracy for properties that are difficult to predict when using physics-based models alone or when limited data is available.

SnO2-Perovskite Interface Engineering Based on Bifacial Passivation via Multifunctional N-(2-Acetamido)-2-aminoethanesulfonic Acid toward Efficient and Stable Solar Cells.

Bifacial passivation on both electron transport materials and perovskite light-absorbing layers as a straightforward technique is used for gaining efficient and stable perovskite solar cells (PSCs). To develop this strategy, organic molecules containing multiple functional groups can maximize the effect of defect suppression. Based on this, we introduce N-(2-acetamido)-2-aminoethanesulfonic acid (ACES) at the interface between tin oxide (SnO2) and perovskite. The synergistic effect of multiple functional groups in ACES, including amino, carbonyl (C═O), and sulfonic acid (S═O) groups, promotes charge extraction of SnO2 and provides an improved energy level alignment for charge transfer. Furthermore, S═O in ACES effectively passivates the defects of uncoordinated Pb2+ in perovskite films, resulting in enhanced crystallinity and decreased nonradiative recombination at the buried interface. The power conversion efficiency (PCE) of related PSCs increases from 20.21% to 22.65% with reduced J-V hysteresis after interface modification with ACES. Notably, upon being stored at a low relative humidity of 40 ± 5% over 2000 h and high relative humidity of 80 ± 5% over 1000 h, the unencapsulated ACES-modified device retains up to 90% and 80% of their initial PCE, respectively. This study deepens defect passivation engineering on the buried interface of perovskites for realizing efficient and stable solar cells.

New mechanism for the participation of aromatic oxidation products in atmospheric nucleation.

Oxygenated organic molecules (OOMs) are recognized as important precursors for new particle formation (NPF) in the urban atmosphere. The paper theoretically studied the formation of OOMs by styrene oxidation processes initiated by OH radicals, focusing on the OOMs nucleation mechanism. The results found that in the presence of an H2SO4 molecule, lowly oxygenated organic molecules containing a benzene ring (LOMBs) can form stable clusters and grow to the scale of a critical nucleus through pi-pi stacking and OH hydrogen bonding. In addition, LOMBs are more readily generated in a styrene-oxidized system in the presence/absence of NOx than highly oxygenated organic molecules (HOMs). The reaction of OH radicals with other aromatics containing a branched chain on the benzene ring produces LOMBs to varying degrees, with pi-pi stacking playing an essential role. This result suggests that, in the presence of H2SO4 molecules, LOMBs may play a more significant role in promoting nucleation than HOMs. Our findings serve as a pivotal foundation for future investigations into the oxidation and nucleation processes of diverse aromatics in urban environments.

Recent synthetic strategies of small heterocyclic organic molecules with optoelectronic applications: a review.

Over the past few years, there have been tremendous developments in the design and synthesis of organic optoelectronic materials with appealing applications in device fabrication of organic light-emitting diodes, superconductors, organic lasers, organic field-effect transistors, clean energy-producing organic solar cells, etc. There is an increasing demand for the synthesis of green, highly efficient organic optoelectronic materials to cope with the issue of efficiency roll-off in organic semiconductor-based devices. This review systematically summarized the recent progress in the design and synthesis of small organic molecules having promising optoelectronic properties for their potential applications in optoelectronic devices during the last 10-year range (2010-early 2021).

Isocyanide-based Multicomponent Reactions (IMCRs) in Water or Aqueous Biphasic Systems.

BACKGROUND: Isocyanide is an intriguing one-carbon synthon that is frequently employed in a variety of carbon-carbon and carbon-heteroatom bond-forming reactions. Isocyanide-based multicomponent reactions (IMCRs) are effective synthetic tools in organic synthesis for the preparation of complex heterocyclic molecules. The IMCRs in water have become an attractive research direction, enabling simultaneous growth of both IMCRs and green solvents towards ideal organic synthesis. OBJECTIVE: The goal of this review is to provide a general overview of IMCRs in water or biphasic aqueous systems for accessing various organic molecules, as well as an examination of their benefits and mechanistic insights. CONCLUSION: High atom economies, mild reaction conditions, high yields, and catalyst-free processes are crucial features of these IMCRs in water or biphasic aqueous systems.

New Insights on the Formation of Nucleation Mode Particles in a Coastal City Based on a Machine Learning Approach.

Atmospheric particles have profound implications for the global climate and human health. Among them, ultrafine particles dominate in terms of the number concentration and exhibit enhanced toxic effects as a result of their large total surface area. Therefore, understanding the driving factors behind ultrafine particle behavior is crucial. Machine learning (ML) provides a promising approach for handling complex relationships. In this study, three ML models were constructed on the basis of field observations to simulate the particle number concentration of nucleation mode (PNCN). All three models exhibited robust PNCN reproduction (R2 > 0.80), with the random forest (RF) model excelling on the test data (R2 = 0.89). Multiple methods of feature importance analysis revealed that ultraviolet (UV), H2SO4, low-volatility oxygenated organic molecules (LOOMs), temperature, and O3 were the primary factors influencing PNCN. Bivariate partial dependency plots (PDPs) indicated that during nighttime and overcast conditions, the presence of H2SO4 and LOOMs may play a crucial role in influencing PNCN. Additionally, integrating additional detailed information related to emissions or meteorology would further enhance the model performance. This pilot study shows that ML can be a novel approach for simulating atmospheric pollutants and contributes to a better understanding of the formation and growth mechanisms of nucleation mode particles.

Oxidized organic molecules in the tropical free troposphere over Amazonia.

New particle formation (NPF) in the tropical free troposphere (FT) is a globally important source of cloud condensation nuclei, affecting cloud properties and climate. Oxidized organic molecules (OOMs) produced from biogenic volatile organic compounds are believed to contribute to aerosol formation in the tropical FT, but without direct chemical observations. We performed in situ molecular-level OOMs measurements at the Bolivian station Chacaltaya at 5240 m above sea level, on the western edge of Amazonia. For the first time, we demonstrate the presence of OOMs, mainly with 4-5 carbon atoms, in both gas-phase and particle-phase (in terms of mass contribution) measurements in tropical FT air from Amazonia. These observations, combined with air mass history analyses, indicate that the observed OOMs are linked to isoprene emitted from the rainforests hundreds of kilometers away. Based on particle-phase measurements, we find that these compounds can contribute to NPF, at least the growth of newly formed nanoparticles, in the tropical FT on a continental scale. Thus, our study is a fundamental and significant step in understanding the aerosol formation process in the tropical FT.

Molecular Composition of Anthropogenic Oxygenated Organic Molecules and Their Contribution to Organic Aerosol in a Coastal City.

Organic aerosols (OA) have gained attention as a substantial component of atmospheric aerosols owing to their impact on atmospheric visibility, climate, and human health. Although oxygenated organic molecules (OOMs) are essential contributors to OA formation, the sources, transformations, and fates of the OOMs are not fully understood. Herein, anthropogenic OOMs (AOOMs), anthropogenic volatile organic compounds (AVOCs), and OA were concurrently measured in Xiamen, a coastal city in southeastern China. Our results show that the AOOMs exhibited a high nitrogen content (76%) and a low oxidation degree. Strong photochemical processes of aromatic VOCs were the predominant sources of AOOMs. Also, NOx concentrations and the occurrence of multigeneration OH radical oxidations were the critical factors that might influence the formation of AOOMs. Finally, the newly developed aerosol dynamic model's results show that more than 35% of the OA mass growth rate is attributed to the gas-particle partitioning of AOOMs. Further sensitivity testing demonstrates that the contribution of AOOMs to OA growth is significantly enhanced during high-particulate-concentration periods, especially under low-temperature conditions. This study emphasizes the vital role of photochemically produced AOOMs derived from AVOCs in OA growth in a coastal urban atmosphere.