Accounting for Cloud Nucleation Activation Mechanism of Secondary Organic Matter from α-Pinene Oxidation Using Experimentally Retrieved Water Solubility Distributions.

Activation of cloud droplets of aerosol particles from biogenic precursors plays a critical role in Earth's climate system. However, the molecular-level understanding of the cloud condensation nuclei (CCN) activation process for secondary organic matter (SOM) is still lacking. Here, we reduced the gap by segregating SOM from α-pinene based on water solubility. The chemical composition and CCN activity of the solubility-segregated fractions of SOM were measured. The results demonstrated for the first time by laboratory experiment that highly oxygenated compounds such as hydroperoxides and highly oxygenated organic molecules are important contributors for the CCN activity of α-pinene SOM. Meanwhile, relatively less water-soluble species were also abundant. Analysis based on the Köhler theory demonstrated that less water-soluble compounds in SOM remain undissolved during the cloud activation process, suggesting that the traditional single-parameter parameterization for CCN activation would not be sufficient for representing the process. In combination with the recent developments in SOM formation chemistry, the present study helps in understanding the interactions between the biosphere and climate.

Enhanced Production of Organosulfur Species during a Severe Winter Haze Episode in the Guanzhong Basin of Northwest China.

The molecular composition of organic aerosols in ambient PM2.5 was investigated in an urban area in the Guanzhong basin of northwest China during a severe regional haze episode in the winter of 2018/2019. Organic matter, accounting for 20-35% of PM2.5 mass concentration, was characterized using direct infusion and electrospray ionization coupled with high-resolution Orbitrap mass spectrometry. The number of organic molecular formula assignments was primarily dominated by organosulfur species (OrgS, including CHOS and CHONS) in negative ion mode. The number and peak signal intensity of OrgS distinctly increased during the severe haze episode. Organosulfates and nitrooxy-organosulfates constituted the majority number (72-94%) of OrgS over the entire period. Although the OrgS were mostly present in aliphatic molecular structures, an increase in the number of polycyclic aromatic OrgS on haze days revealed the enhanced contribution from anthropogenic sources. The number of OrgS strongly correlated with ambient relative humidity and the oxidation ratios of sulfur and nitrogen, suggesting the important roles of aqueous phase chemistry and atmospheric oxidation in the formation of OrgS. A thorough understanding of the significance of OrgS will be essential to assess and mitigate the adverse impacts of haze pollution.

Cascade reaction triggering and photothermal AuNPs@MIL MOFs doped intraocular lens for enhanced posterior capsular opacification prevention.

Posterior capsular opacification (PCO) is the most common complication after cataract surgery. Present strategies can't meet the clinical needs of long-term prevention. This research reports a novel intraocular lens (IOL) bulk material with high biocompatibility and synergistic therapy. Gold nanoparticles (AuNPs) doped MIL-101-NH2 metal-organic frameworks (MOFs) (AuNPs@MIL) was firstly fabricated via in situ reductions. Then the functionalized MOFs were uniformly mixed with glycidyl methacrylate (GMA) and 2-(2-ethoxyethoxy) ethyl acrylate (EA) to form the nanoparticle doped polymer (AuNPs@MIL-PGE), and which was used to fabricate IOL bulk materials. The materials' optical and mechanical properties with different mass contents of nanoparticles are investigated. Such bulk functionalized IOL material could efficiently remove residual human lens epithelial cells (HLECs) in the capsular bag in the short term, and can prevent PCO on demand in the long run by near-infrared illumination (NIR) action. In vivo and in vitro experiments demonstrate the biosafety of the material. The AuNPs@MIL-PGE exhibits excellent photothermal effects, which could inhibit cell proliferation under NIR and doesn't cause pathological effects on the surrounding tissues. Such functionalized IOL can not only avoid the side effects of the antiproliferative drugs but also realize the enhanced PCO prevention in clinical practice.

NIR-triggered thermosensitive polymer brush coating modified intraocular lens for smart prevention of posterior capsular opacification.

Posterior capsule opacification (PCO) is the most common complication after cataract surgery. Drug-eluting intraocular lens (IOLs) is a promising concept of PCO treatment in modern cataract surgery. However, the large dose of drugs in IOL leads to uncontrollable and unpredictable drug release, which inevitably brings risks of overtreatment and ocular toxicity. Herein, a low-power NIR-triggered thermosensitive IOL named IDG@P(NIPAM-co-AA)-IOL is proposed to improve security and prevent PCO by synergetic controlled drug therapy and simultaneous photo-therapy. Thermosensitive polymer brushes Poly(N-isopropylacrylamide-co-Acrylic acid) (P(NIPAM-co-AA)) is prepared on IOL via surface-initiated reversible addition-fragmentation chain transfer (SI-RAFT) polymerization. Then, Doxorubicin (DOX) and Indocyanine green (ICG) co-loaded Gelatin NPs (IDG NPs) are loaded in P(NIPAM-co-AA) by temperature control. The IDG NPs perform in suit photodynamic & photothermal therapy (PTT&PDT), and the produced heat also provides a trigger for controllable drug therapy with a cascade effect. Such functional IOL shows excellent synergistic drug-phototherapy effect and NIR-triggered drug release behavior. And there is no obvious PCO occurrence in IDG@P(NIPAM-co-AA) IOL under NIR irradiation compared with control group. This proposed IDG@P(NIPAM-co-AA)-IOL serves as a promising platform that combines phototherapy and drug-therapy to enhance the therapeutic potential and medication safety for future clinical application of PCO treatment.

Transcriptome-phenotype matching analysis of how nitrogen sources influence Lacticaseibacillus rhamnosus tolerance to heat stress and oxidative stress.

BACKGROUND: Spray drying is the most cost-effective production method for lactic acid bacteria starters, but heat and oxidative stresses result in low survival rates. The heat stress and oxidative stress tolerance of Lacticaseibacillus rhamnosus cultured in tryptone-free MRS (NP-MRS) broth was much stronger than that in MRS or tryptone-free MRS broth supplemented with phenylalanine (Phe-MRS). Here, multiple transcriptome-phenotype matching was performed on cells cultured in NP-MRS, MRS and Phe-MRS broths to reveal the mechanism by which nitrogen sources influence L. rhamnosus tolerance to heat stress and oxidative stress. RESULTS: Compared with cells cultured in NP-MRS broth, 83 overlapping differentially expressed genes (DEGs) were downregulated by either tryptone or phenylalanine. The overlapping DEGs were mainly classified into carbohydrate metabolism and membrane transport pathways, which are often repressed by glucose during carbon catabolite repression (CCR). In the presence of glucose, the heat stress or oxidative stress tolerance of L. rhamnosus hsryfm 1301 was not strengthened by supplementation with secondary carbohydrates. Replacing glucose with mannose, fructose or ribose improved the heat stress and oxidative stress tolerance of L. rhamnosus hsryfm 1301 (5 to 46-fold). CONCLUSIONS: Alleviation of CCR might be a reason for the resistance of L. rhamnosus hsryfm 1301 to heat stress and oxidative stress in a low-nitrogen environment. The survival rate of L. rhamnosus during spray drying will hopefully be improved by relieving CCR. It is a new discovery that nitrogen sources influence CCR in L. rhamnosus.

Oil sands operations as a large source of secondary organic aerosols.

Worldwide heavy oil and bitumen deposits amount to 9 trillion barrels of oil distributed in over 280 basins around the world, with Canada home to oil sands deposits of 1.7 trillion barrels. The global development of this resource and the increase in oil production from oil sands has caused environmental concerns over the presence of toxic compounds in nearby ecosystems and acid deposition. The contribution of oil sands exploration to secondary organic aerosol formation, an important component of atmospheric particulate matter that affects air quality and climate, remains poorly understood. Here we use data from airborne measurements over the Canadian oil sands, laboratory experiments and a box-model study to provide a quantitative assessment of the magnitude of secondary organic aerosol production from oil sands emissions. We find that the evaporation and atmospheric oxidation of low-volatility organic vapours from the mined oil sands material is directly responsible for the majority of the observed secondary organic aerosol mass. The resultant production rates of 45-84 tonnes per day make the oil sands one of the largest sources of anthropogenic secondary organic aerosols in North America. Heavy oil and bitumen account for over ten per cent of global oil production today, and this figure continues to grow. Our findings suggest that the production of the more viscous crude oils could be a large source of secondary organic aerosols in many production and refining regions worldwide, and that such production should be considered when assessing the environmental impacts of current and planned bitumen and heavy oil extraction projects globally.

Influence of nitrogen sources on the tolerance of Lacticaseibacillus rhamnosus to heat stress and oxidative stress.

It has been found that 32 genes related to nitrogen source metabolism in Lacticaseibacillus rhamnosus are downregulated under both heat stress and oxidative stress. In this study, the influence of different nitrogen sources within the growth medium on the tolerance of L. rhamnosus to heat stress and oxidative stress was investigated. Tryptone-free MRS was found to enhance the tolerance of L. rhamnosus hsryfm 1301 to heat stress and oxidative stress during the whole growth period, and this result was universal for all L. rhamnosus species analyzed. The strongest strengthening effect occurred when the OD600 value reached 2.0, at which the survival rates under heat stress and oxidative stress increased 130-fold and 40-fold, respectively. After supplementing phenylalanine, isoleucine, glutamate, valine, histidine, or tryptophan into the tryptone-free MRS, the tolerance of L. rhamnosus to heat stress and oxidative stress exhibited a sharp drop. The spray drying survival rate of L. rhamnosus hsryfm 1301 cultured in the tryptone-free MRS rose to 75% (from 30%), and the spray dried powder also performed better in the experimentally simulated gastrointestinal digestion. These results showed that decreasing the intake of amino acids is an important mechanism for L. rhamnosus to tolerate heat stress and oxidative stress. When L. rhamnosus is cultured for spray drying, the concentration of the nitrogen source's components should be an important consideration.

Humidity Dependence of the Condensational Growth of α-Pinene Secondary Organic Aerosol Particles.

The influence of relative humidity (RH) on the condensational growth of organic aerosol particles remains incompletely understood. Herein, the RH dependence was investigated via a series of experiments for α-pinene ozonolysis in a continuously mixed flow chamber in which recurring cycles of particle growth occurred every 7 to 8 h at a given RH. In 5 h, the mean increase in the particle mode diameter was 15 nm at 0% RH and 110 nm at 75% RH. The corresponding particle growth coefficients, representing a combination of the thermodynamic driving force and the kinetic resistance to mass transfer, increased from 0.35 to 2.3 nm2 s-1. The chemical composition, characterized by O:C and H:C atomic ratios of 0.52 and 1.48, respectively, and determined by mass spectrometry, did not depend on RH. The Model for Simulating Aerosol Interactions and Chemistry (MOSAIC) was applied to reproduce the observed size- and RH-dependent particle growth by optimizing the diffusivities Db within the particles of the condensing molecules. The Db values increased from 5 α-1 × 10-16 at 0% RH to 2 α-1 × 10-12 cm-2 s-1 at 75% RH for mass accommodation coefficients α of 0.1 to 1.0, highlighting the importance of particle-phase properties in modeling the growth of atmospheric aerosol particles.

Environmentally Persistent Free Radical (EPFR) Formation by Visible-Light Illumination of the Organic Matter in Atmospheric Particles.

A secondary process may be an important source of environmentally persistent free radicals (EPFRs) in atmospheric particulates; yet, this process remains to be elucidated. This study demonstrated that secondary EPFRs could be generated by visible-light illumination of atmospheric particulate matter (PM), and their lifetimes were only 30 min to 1 day, which were much shorter than the lifetimes of the original EPFRs in PM. The yields of secondary EPFRs produced by PM could reach 15-60% of those of the original EPFRs. The extractable organic matter contributed to the formation of secondary EPFRs (∼55%), and a humic-like substance was the main precursor of the secondary EPFRs and was also the most productive precursor compared to the other aerosol components. The results of simulation experiments showed that the secondary EPFRs generated by the extractable and nonextractable PM components were similar to those produced by phenolic compounds and polycyclic aromatic hydrocarbons, respectively. We have found that oxygen molecules play an important role in the photochemical generation and decay of EPFRs. The reactive oxygen capture experiments showed that the original EPFRs may contribute to singlet oxygen generation, while the secondary EPFRs generated by photoexcitation may not produce singlet oxygen or hydroxyl radicals.

Quantifying the Role of the Relative Humidity-Dependent Physical State of Organic Particulate Matter in the Uptake of Semivolatile Organic Molecules.

The uptake of gas-phase dicarboxylic acids to organic particulate matter (PM) was investigated to probe the role of the PM physical state in exchange processes between gas-phase semivolatile organic molecules and organic PM. A homologous series of probe molecules, specifically isotopically labeled 13C-dicarboxylic acids, was used in conjunction with aerosol mass spectrometry to obtain a quantitative characterization of the uptake to organic PM for different relative humidities (RHs). The PM was produced by the dark ozonolysis of unlabeled α-pinene. The uptake of 13C-labeled oxalic, malonic, and α-ketoglutaric acids increased stepwise by 5 to 15 times with increases in RH from 15 to 80%. The enhanced uptake with increasing RH was explained primarily by the higher molecular diffusivity in the particle phase, as associated with changes in the physical state of the organic PM from a nonliquid state to a progressively less-viscous liquid state. At high RH, the partitioning of the probe molecules to the particle phase was more associated with physicochemical interactions with the organic PM than that with the co-absorbed liquid water. Uptake of the probe molecules also increased with a decrease in volatility along the homologous series. This study quantitatively shows the key roles of the particle physical state in governing the interactions of organic PM with semivolatile organic molecules.

Oxidative Potential of Water-Soluble Matter Associated with Chromophoric Substances in PM2.5 over Xi'an, China.

Organic compounds are important contributors to the oxidative potential (OP) of atmospheric aerosols. This study is the first to report the OP of water-soluble organic matter (WSOM) related to the chromophoric substances in PM2.5 over Xi'an, China. The dithiothreitol (DTT) activity levels in PM2.5 extracted by water were quantified as well as the relationships between DTT activity and light absorption and fluorescence properties. The results show that the DTT activity has significantly correlated with colored WSOM, in which we identified three light absorbing substances (BrC1-3) and eight fluorescent substances (C1-8). It is further found that BrC3 and C7 accounted for almost all of the DTT activity by colored WSOM, although these two factors contributed only a small fraction of light absorption and fluorescence. BrC3 and C7 are clearly distinguished from other chromophoric substances because of their long absorption wavelength (λmax = 475 nm) and fluorescence emission wavelength (λmax = 462 nm), respectively. This discovery will help to better interpret and understand the mechanism of oxidation activity generation by light absorbing organic aerosols and provide guidance for predicting the OPs of light absorbing organic aerosols based on their optical properties.

Influence of Particle Surface Area Concentration on the Production of Organic Particulate Matter in a Continuously Mixed Flow Reactor.

Organic particulate matter (PM) was produced at different particle surface area concentrations S in a continuously mixed flow reactor (CMFR). The apparent PM yield from the dark ozonolysis of α-pinene increased from 24.5 ± 0.7% to 57.1 ± 0.6% for an increase in S from 0.55 to 2.87 × 103 µm2·surface cm-3·volume. The apparent yield saturated for S > 2.1 × 103 µm2 cm-3. There was hysteresis in the apparent yield for experiments of increasing compared to decreasing S. The relative timescales of gas-particle interactions, gas-wall interactions, and thereby particle-wall cross interactions could explain the results. The PM carbon oxidation state and oxygen-to-carbon atomic ratio decreased from -0.19 to -0.47 and 0.62 to 0.51, respectively, for increasing S, suggesting that greater partitioning of semivolatile organic species into the PM contributed to the increased PM yield. A thorough understanding of the role of gas-wall interactions on apparent PM yield is essential for the extension of laboratory results into predictions of atmospheric PM production, and comparative results from CMFRs and batch reactors can be informative in this regard.

Influence of Particle Physical State on the Uptake of Medium-Sized Organic Molecules.

The uptake of medium-sized levoglucosan and 2,4-dinitrophenol to organic particles produced by α-pinene ozonolysis and to ammonium sulfate particles was studied from 10% to >95% relative humidity (RH). For aqueous sulfate particles, the water-normalized gas-particle partitioning coefficient of levoglucosan decreased from (1.0 ± 0.1) × 10-3 to (0.2 ± 0.1) × 10-3 (ng µg-1)particle/(ng m-3)gas from 40% to >95% RH, suggestive of a salting-in mechanism between levoglucosan and ionic ammonium sulfate solutions. For the organic particles, the levoglucosan partitioning coefficient increased from 10% to 40% RH and became invariant at (2.0 ± 0.4) × 10-3 (ng µg-1)/(ng m-3) above 40% RH. A kinetic limitation on uptake below 40% RH was implied, compared to a thermodynamic regime above 40% RH. The estimated diffusivity was 10-19±0.05 m2 s-1 at 40% RH. By comparison, the uptake of 2,4-dinitrophenol onto the organic particles was below detection limit, implying an upper limit on the partitioning coefficient of 6.8 × 10-6 (ng µg-1)/(ng m-3) at 80% RH. The results highlight that the molecular uptake of gases onto particles can be regulated by both kinetic and thermodynamic factors, either of which can limit the uptake of medium-sized organic molecules by atmospherically relevant particles.

Nitrogen removal via a single-stage PN-Anammox process in a novel combined biofilm reactor.

This study developed a partial nitrification (PN) and anaerobic ammonia oxidation (Anammox) process for treating high-ammonia wastewater using an innovative biofilm system in which ammonia oxidizing bacteria grew on fluidized Kaldnes (K1) carriers and Anammox bacteria grew on fixed acryl resin carriers. The airlift loop biofilm reactor (ALBR) was stably operated for more than 4 months under the following conditions: 35 ± 2 °C, pH 7.5-8.0 and dissolved oxygen (DO) of 0.5-3.5 mg/L. The results showed that the total nitrogen removal efficiency reached a maximum of 75% and the total nitrogen removal loading rate was above 0.4 kg/(d·m3). DO was the most efficient control parameter in the mixed biofilm system, and values below 1.5 mg/L were observed in the riser zone for the PN reaction, while values below 0.8 mg/L were observed in the downer zone for the Anammox reaction. Scanning electron microscopy and Fluorescence In Situ Hybridization images showed that most of the nitrifying bacteria were distributed on the K1 carriers and most of the Anammox bacteria were distributed within the acryl resin carriers. Therefore, the results indicate that the proposed combined biofilm system is easy to operate and efficient for the treatment of high-ammonia wastewater.

Thermo-sensitive Poloxamer based antibacterial anti-inflammatory and photothermal conductive multifunctional hydrogel as injectable, in situ curable and adjustable intraocular lens.

Cataract patients look forwards to fewer postoperative complications and higher vision quality after surgery. However, the current intraocular lens (IOL) implanted after cataract surgery neither can adjust focal length in response to ciliary muscle contraction as natural lens nor have the ability to prevent postoperative complications. Herein, a thermosensitve Poloxamer based hybrid hydrogel with antibacterial anti-inflammatory and photothermal functional elements doping was designed and used as injectable, in situ curable, and adjustable IOL (FHTAB IOL). The FHTAB IOL was composed of thermosensitve triblock-polymer F127DA and a small amount of HAMA, combined with BP NS, TA, and Ag NPs. FHTAB IOL can be injected into the empty lens capsule after cataract surgery via an injectable thermos-gel under NIR illumination and then be rapidly cured to form a full-size IOL under short-time blue light irradiation. The designed injectable FHTAB IOL possesses high transparency and transmittance, with a refractive index similar to the natural lens and adjustable properties. It was stabilized as a refractive medium without any leakage in the eye. In addition, the TA and Ag NPs loaded in the FHTAB IOL displayed significant antibacterial and anti-inflammatory effects in vitro and vivo. This study presents a potentially effective new strategy for the development of multifunctional adjustable IOLs.

Correction: Ocular biocompatibility evaluation of POSS nanomaterials for biomedical material applications.

[This corrects the article DOI: 10.1039/C5RA08668J.].

Variability in molecular composition and optical absorption of atmospheric brown carbon aerosols in two contrasting urban areas of China.

Atmospheric brown carbon (BrC) aerosols were investigated at two urban sites in southern (Hefei) and northern (Shijiazhuang) China during summer and winter of 2019-2020 to explore regional variability in their compositional and optical properties. Organic matter in ambient PM2.5 samples were characterized at molecular level using ultrahigh performance liquid chromatography coupled with a diode array detector and an Orbitrap mass spectrometer. Although the molecular composition of organic aerosols varied substantially over different ambient environments, they were mainly composed by CHO and CHON species in positive ionization mode while CHO and CHOS species in negative mode. The mass absorption coefficients of BrC aerosols at wavelength range 250-450 nm were relatively higher for winter samples in both cities and for Shijiazhuang samples in both seasons, partly attributed to the higher concentration levels of anthropogenic air pollutants in these environments. The absorption Ångström exponents further revealed that BrC aerosols in winter seasons and in Shijiazhuang had a greater capacity of absorption at shorter wavelengths. A total of 26 BrC species with strong absorption were unambiguously identified from different environments, which mainly consisted of CHO, CHON, and CHN species and had higher degrees of unsaturation and lower degrees of oxidation. The presence and abundance of these BrC species varied dynamically across the seasons and cities, with a greater number of species presented in the winter of Shijiazhuang. The BrC species together contributed 12-26 % in the total absorbance of light-absorbing organic components at 250-450 nm. This study highlights the regional differences in BrC properties influenced by the sources and atmospheric processes, which should be taken into account to assess their climate impacts.

Effects of photochemical aging on the molecular composition of organic aerosols derived from agricultural biomass burning in whole combustion process.

Biomass burning organic aerosols (BBOA) are key components of atmospheric particulate matter, yet the effects of aging process on their chemical composition and related properties remain poorly understood. In this study, fresh smoke emissions from the combustion of three types of agricultural biomass residues (rice, maize, and wheat straws) were photochemically aged in an oxidation flow reactor. The changes in BBOA composition were characterized by offline analysis using ultrahigh performance liquid chromatography coupled with Orbitrap mass spectrometry. The BBOA molecular composition varied dramatically with biomass type and aging process. Fresh and aged BBOA were predominated by CHO and nitrogen-containing CHON, CHN, and CHONS species, while with very few CHOS and other non­oxygen species. The signal peak area variations revealed that individual molecular species underwent dynamic changes, with 77-81 % of fresh species decreased or even disappeared and 33-46 % of aged species being newly formed. A notable increase was observed in the number and peak area of CxHyO≥6 compounds in aged BBOA, suggesting that photochemical process served as an important source of highly oxygenated species. Heterocyclic CxHyN2 compounds mostly dominated in fresh CHN species, whereas CxHyN1 were more abundant in aged ones. Fragmentation and homologs oxidation by addition of oxygen-containing functional groups were important pathways for the BBOA aging. The changes in BBOA composition with aging would have large impacts on particle optical properties and toxicity. This study highlights the significance of photochemical aging process in altering chemical composition and related properties of BBOA.

Photo-controllable drug releasing bulk polyacrylic intraocular lens material for safer posterior capsular opacification prevention.

Posterior capsular opacification (PCO) is the most common complication that occurs after intraocular lens (IOL) implantation in cataract therapy. In recent years, IOLs have been developed as drug delivery platforms, but concerns over the safety of uncontrolled proliferative drug release have arisen. Therefore, a controlled drug release strategy is needed for safer PCO prevention. In this study, a new monomer contained coumarin group was introduced in material preparation, and poly(ethylene glycol phenyl ether methacrylate-co-2-(2-ethoxyethoxy) ethyl acrylate-co-7-(2-methacryloyloxyethoxy)-4-methylcoumarin) (PEEC) acrylic IOL materials were synthesized. The antiproliferative drug 5-fluorouracil (5-FU) could be chemically grafted to the PEEC IOL materials easily via a light induced [2 + 2] cycloaddition reaction with the coumarin group, getting drug-loaded IOL (PEEC@5-FU IOL). The PEEC@5-FU IOL exhibited excellent optical and mechanical properties and biocompatibility. More importantly, the loaded 5-FU could be easily controlled from release by light irradiation via photo-dissociation of the cyclobutane ring that was obtained by the [2 + 2] cycloaddition reaction of 5-FU and coumarin. The in vitro and in vivo experiments demonstrated that such photo-controllable drug release IOL could effectively prevent PCO after implantation in a safe way.

Expression of Concern: Surface modification of intraocular lenses via photodynamic coating for safe and effective PCO prevention.

Expression of Concern for 'Surface modification of intraocular lenses via photodynamic coating for safe and effective PCO prevention' by Junmei Tang et al., J. Mater. Chem. B, 2021, 9, 1546-1556, https://doi.org/10.1039/D0TB02802A.