Insight into the Mechanism and Kinetics of the Heterogeneous Reaction between SO2 and NO2 on Diesel Black Carbon under Light Irradiation.

The heterogeneous oxidation of SO2 by NO2 has been extensively proposed as an important pathway of sulfate production during haze events in China. However, the kinetics and mechanism of oxidation of SO2 by NO2 on the surface of complex particles remain poorly understood. Here, we systematically explore the mechanism and kinetics of the reaction between SO2 and NO2 on diesel black carbon (DBC) under light irradiation. The experimental results prove that DBC photochemistry can not only significantly promote the heterogeneous reduction of NO2 to produce HONO via transferring photoinduced electrons but also indirectly promote OH radical formation. These reduction products of NO2 as well as NO2 itself greatly promote the heterogeneous oxidation of SO2 on DBC. NO2 oxidation, HONO oxidation, and the surface photo-oxidation process are proven to be three major surface oxidation pathways of SO2. The kinetics results indicate that the surface photooxidation pathway accounts for the majority of the total SO2 uptake (∼63%), followed by the HONO oxidation pathway (∼27%) and direct oxidation by NO2 (∼10%). This work highlights the significant synergistic roles of DBC, NO2, and light irradiation in enhancing the atmospheric oxidation capacity and promoting the heterogeneous formation of sulfate.

Evaluation of effects of 3% diquafosol ophthalmic solution on preocular tear film stability after trabeculectomy.

OBJECTIVES: To determine the potential effects of 3% diquafosol (DQS) on tear film stability after glaucoma surgery. METHODS: We retrospectively reviewed consecutive patients who underwent glaucoma surgery at the glaucoma division of the Henan Eye Institute from January 2020 to January 2021. Clinical parameters, including age, sex, intraocular pressure, and number of glaucoma medications, were tested. Tear film parameters, such as tear meniscus height (TMH), first and average noninvasive tear break-up time (FBUT and ABUT, respectively), and tear film lipid layer grade (TFLL), were evaluated using the Oculus Keratograph 5M. We investigated the differences in clinical and tear film parameters pre- and postoperatively. We compared the baseline and different time points after surgery between the DQS and HA groups and identified the factors associated with changes in the tear film at 8 weeks postoperatively. RESULTS: A total of 101 eyes were included. Early administration of DQS increased TMH, FBUT, ABUT, and TFLL after trabeculectomy (all p < 0.05). In addition, the DQS group showed significantly higher ABUT than the HA group (p < 0.05). DQS use served as an associated parameter for better TMH, FBUT, ABUT, and the TFLL (p < 0.05). DQS and preoperative FBUT were significant independent parameters of postoperative FBUT (p < 0.05). CONCLUSIONS: The present study showed that postoperative TMH, FBUT, ABUT, and TFLL significantly increased after early application of DQS, and the efficacy of ABUT was better than that of HA at the early stage in 8 weeks after trabeculectomy (p < 0.05).

Heterogeneous kinetics of the OH-initiated degradation of fenthion and parathion.

Fenthion and parathion are two representative kinds of organophosphorus pesticides and widely used in agriculture. They are directly or indirectly released into the atmosphere by spraying or volatilization processes. However, their heterogeneous reactivity toward OH radicals has not yet been well understood. Therefore, this work investigated the heterogeneous kinetics of the OH-initiated degradation of surface-bound fenthion and parathion using a flow reactor. The results showed that OH radicals played an important role in the atmospheric degradation of fenthion and parathion. Their average rate constants were (7.20 ± 0.77) × 10-12 and (10.40 ± 0.60) × 10-12 cm3/(mol· sec) at a relative humidity (RH) and temperature of 35% and 20 °C, respectively, suggesting that they have relatively short lifetimes in the atmosphere. In addition, a negative RH dependence and a positive temperature dependence of the rate constants were observed. The Arrhenius expressions of fenthion and parathion were k2 = (1.34 ± 0.48) × 10-9exp[-(1432.59 ± 105.29)/T] and k2 = (1.96 ± 1.38) × 10-9exp[-(1619.98 ± 222.02)/T], respectively, and their overall activation energy was estimated to be (11.88 ± 0.87) and (13.48 ± 1.83) kJ/mol. The experimental results will update the kinetic data of fenthion and parathion in the atmosphere and be helpful to further understand their atmospheric transportation processes.

Circ_NNT suppresses the apoptosis and inflammation in glucose-induced human retinal pigment epithelium by regulating miR-320b/TIMP3 axis in diabetic retinopathy.

BACKGROUND: Diabetic retinopathy (DR) is a frequent complication of diabetes. Recent reports have showed that circular RNAs (circRNAs) play important roles in DR progression. Herein, the aim of this study was to explore the role and molecular mechanism of circ_NNT in DR process. METHODS: Human retinal pigment epithelial cells ARPE-19 were treated with high glucose (HG) in experimental group. The expression of circ_NNT, miR-320b, and TIMP3 (TIMP Metallopeptidase Inhibitor 3) were determined using quantitative real-time polymerase chain reaction and Western blot. In vitro experiments were conducted by 5-ethynyl-2'-deoxyuridine (EdU) assay, MTT assay, flow cytometry, Western blot, and ELISA. The binding interaction was confirmed using dual-luciferase reporter and pull-down assays. RESULTS: HG stimulation led to a decrease of circ_NNT and TIMP3 expression, and an increase of miR-320b expression in ARPE-19 cells. Functionally, circ_NNT up-regulation reversed HG-evoked apoptosis and inflammation in ARPE-19 cells. Mechanistically, circ_NNT acted as a sponge for miR-320b to elevate TIMP3 expression. Further rescue experiments showed that miR-320b elevation attenuated the protective effects of circ_NNT on HG-induced ARPE-19 cells. Moreover, inhibition of miR-320b protected ARPE-19 cells against HG-evoked apoptosis and inflammation, which were abolished by TIMP3 knockdown. CONCLUSION: Circ_NNT protected ARPE-19 cells against HG-evoked apoptosis and inflammation via elevating TIMP3 through sequestering miR-320b, indicating that up-regulation of circ_NNT might contribute to the inhibition of DR process.

Atmospheric Reactivity of Methoxyphenols: A Review.

Methoxyphenols emitted from lignin pyrolysis are widely used as potential tracers for biomass burning, especially for wood burning. In the past ten years, their atmospheric reactivity has attracted increasing attention from the academic community. Thus, this work provides an extensive review of the atmospheric reactivity of methoxyphenols, including their gas-phase, particle-phase, and aqueous-phase reactions, as well as secondary organic aerosol (SOA) formation. Emphasis was placed on kinetics, mechanisms, and SOA formation. The reactions of methoxyphenols with OH and NO3 radicals were the predominant degradation pathways, which also had significant SOA formation potentials. The reaction mechanism of methoxyphenols with O3 is the cycloaddition of O3 to the benzene ring or unsaturated C═C bond, while H-abstraction and radical adduct formation are the main degradation channels of methoxyphenols by OH and NO3 radicals. Based on the published studies, knowledge gaps were pointed out. Future studies including experimental simulations and theoretical calculations of other representative kinds of methoxyphenols should be systematically carried out under complex pollution conditions. In addition, the ecotoxicity of their degradation products and their contribution to SOA formation from the atmospheric aging of biomass-burning plumes should be seriously assessed.

Secondary Organic Aerosol Formation Potential from Ambient Air in Beijing: Effects of Atmospheric Oxidation Capacity at Different Pollution Levels.

Secondary organic aerosol (SOA) plays a critical role in sustained haze pollution in megacities. Traditional observation of atmospheric aerosols usually analyzes the ambient organic aerosol (OA) but neglects the SOA formation potential (SOAFP) of precursors remaining in ambient air. Knowledge on SOAFP is still limited, especially in megacities suffering from frequent haze. In this study, the SOAFP of ambient air in urban Beijing was characterized at different pollution levels based on a two-year field observation using an oxidation flow reactor (OFR) system. Both OA and SOAFP increased as a function of ambient pollution level, in which increasing concentrations of precursor volatile organic compounds (VOCs) and decreasing atmospheric oxidation capacity were found to be the two main influencing factors. To address the role of the atmospheric oxidation capacity in SOAFP, a relative OA enhancement ratio (EROA = 1 + SOAFP/OA) and the elemental composition of the OA were investigated in this study. The results indicated that the atmospheric oxidation capacity was weakened and resulted in higher SOAFP on more polluted days. The relationship found between SOAFP and the atmospheric oxidation capacity could be helpful in understanding changes in SOA pollution with improving air quality in the megacities of developing countries.

Impacts of SO2, Relative Humidity, and Seed Acidity on Secondary Organic Aerosol Formation in the Ozonolysis of Butyl Vinyl Ether.

Alkyl vinyl ethers are widely used as fuel additives. Despite this, their atmospheric chemistry and secondary organic aerosol (SOA) formation potentials are still not well-known under complex pollution conditions. In this work, we examined the impact of SO2, relative humidity (RH), and particle acidity on the formation and oxidation state (OSc) of SOA from butyl vinyl ether (BVE) ozonolysis. Increasing SO2 concentration produced a notable promotion of SOA formation and OSc due to the significant increase in H2SO4 particles and formation of more highly oxidized components. Increased RH in the presence of SO2 appeared to promote, suppress, and dominate the formation and OSc of SOA in the dry range (1-10%), low RH range (10-42%), and moderate RH range (42-64%), respectively. This highlights the importance of competition between H2O and SO2 in reacting with the stabilized Criegee intermediate in BVE ozonolysis at ambient RH. Increased particle acidity mainly contributed to the change in chemical composition of BVE-dominated SOA but not to SOA formation. The results presented here extend previous analysis of BVE-derived SOA and further aid our understanding of SOA formation potential of BVE ozonolysis under highly complex pollution conditions.

Differences of the oxidation process and secondary organic aerosol formation at low and high precursor concentrations.

Current atmospheric quality models usually underestimate the level of ambient secondary organic aerosol (SOA), one of the possible reasons is that the precursors at different concentrations may undergo different oxidation processes and further affect SOA formation. Therefore, there is a need to perform more chamber studies to disclose the influence. In this work, SOA formation over a wide range of initial precursor concentrations (tens of ppb to hundreds of ppb levels) was investigated in a 30 m3 indoor smog chamber, and mainly through the analysis of multiple generations of VOCs detected from HR-ToF-PTRMS to expound the difference in the oxidation process between low and high precursor concentrations. Compared to high initial concentrations, gas-phase intermediates formed at low concentrations had a higher intensity by about one order of magnitude, and the low-volatility compounds also had a higher formation potential due to the competition between semi-volatile intermediates and precursors with oxidants. In addition, the formed SOA was more oxidized with higher f44 value (0.14 ±â€¯0.02) and more relevant to real atmosphere than that formed at high concentrations. This work should help to deeply understand SOA formation and improve the performance of air quality models for SOA simulation.

Near-infrared light-guided miniaturized indirect ophthalmoscopy for nonmydriatic wide-field fundus photography.

A portable fundus imager is essential for emerging telemedicine screening and point-of-care examination of eye diseases. However, existing portable fundus cameras have limited field of view (FOV) and frequently require pupillary dilation. We report here a miniaturized indirect ophthalmoscopy-based nonmydriatic fundus camera with a snapshot FOV up to 67° external angle, which corresponds to a 101° eye angle. The wide-field fundus camera consists of a near-infrared light source (LS) for retinal guidance and a white LS for color retinal imaging. By incorporating digital image registration and glare elimination methods, a dual-image acquisition approach was used to achieve reflection artifact-free fundus photography.

Secondary Organic Aerosol Formation from Ambient Air at an Urban Site in Beijing: Effects of OH Exposure and Precursor Concentrations.

Secondary organic aerosol (SOA) is an important component of atmospheric fine particles (PM2.5), while the key factors controlling SOA formation in ambient air remain poorly understood. In this work, the SOA formation in Beijing urban ambient air was investigated using an oxidation flow reactor (OFR) with high concentrations of OH radicals. The SOA formation potential increased significantly with the increase of ambient PM2.5 concentration during the observation. The optimum ambient exposure time, which is the aging time equivalent to atmospheric oxidation (with similar OH exposure) associated with the peak SOA formation, varied between 2 and 4 days in this study. The OA enhancement in this study was much higher than that of developed countries under different environmental conditions. The higher OA enhancement is probably due to the higher concentrations of volatile organic compounds (VOCs) in the urban air of Beijing. This might also have occurred because fragmentation did not dominate in the oxidation of OA, and did not result in negative OA enhancement on highly polluted days compared to relatively clean days with similar exposure time. These results suggested that under typical ambient conditions, high concentrations of VOC precursors might contribute to sustained organic aerosol growth and long duration haze events in Beijing.

Selective and Cleavable Extraction of Sialo-glycoproteins by Disulfide-Linked Amino-oxy-Functionalized Fe3O4 Magnetic Nanoparticles.

The low abundance of sialo-glycoprotein hampered the separation, enrichment, and analysis of sialo-glycoproteins, which are critical for studying their functions. Here, we designed cleavable amino-oxy functionalized magnetic materials and employed to fast and selective isolate sialo-glycoproteins. This includes the ligation of disulfide-linked amino-oxy-functionalized magnetic nanoparticles with periodate-treated glycoproteins or cells, followed by magnetic separation. A reductive reagent could release the sialo-glycoproteins with small molecular fragments on the terminal of glycan chains, and the sialo-glycoproteins were analyzed by sodium dodecyl sulfate polyacrylamide gel electrophoresis. On-bead digestion of the peptides were analyzed by tandem mass spectrometry. The results indicated that this method could selectively separate the majority of cell-surface sialo-glycoproteins.

Digital adaptive optics confocal microscopy based on iterative retrieval of optical aberration from a guidestar hologram.

Guidestar hologram based digital adaptive optics (DAO) is one recently emerging active imaging modality. It records each complex distorted line field reflected or scattered from the sample by an off-axis digital hologram, measures the optical aberration from a separate off-axis digital guidestar hologram, and removes the optical aberration from the distorted line fields by numerical processing. In previously demonstrated DAO systems, the optical aberration was directly retrieved from the guidestar hologram by taking its Fourier transform and extracting the phase term. For the direct retrieval method (DRM), when the sample is not coincident with the guidestar focal plane, the accuracy of the optical aberration retrieved by DRM undergoes a fast decay, leading to quality deterioration of corrected images. To tackle this problem, we explore here an image metrics-based iterative method (MIM) to retrieve the optical aberration from the guidestar hologram. Using an aberrated objective lens and scattering samples, we demonstrate that MIM can improve the accuracy of the retrieved aberrations from both focused and defocused guidestar holograms, compared to DRM, to improve the robustness of the DAO.

High-speed line-field confocal holographic microscope for quantitative phase imaging.

We present a high-speed and phase-sensitive reflectance line-scanning confocal holographic microscope (LCHM). We achieved rapid confocal imaging using a fast line-scan CCD camera and quantitative phase imaging using off-axis digital holography (DH) on a 1D, line-by-line basis in our prototype experiment. Using a 20 kHz line scan rate, we achieved a frame rate of 20 Hz for 512x512 pixels en-face confocal images. We realized coherent holographic detection two different ways. We first present a LCHM using off-axis configuration. By using a microscope objective of a NA 0.65, we achieved axial and lateral resolution of ~3.5 micrometers and ~0.8 micrometers, respectively. We demonstrated surface profile measurement of a phase target at nanometer precision and the digital refocusing of a defocused confocal en-face image. Ultrahigh temporal resolution M mode is demonstrated by measuring the vibration of a PZT-actuated mirror driven by a sine wave at 1 kHz. We then report our experimental work on a LCHM using an in-line configuration. In this in-line LCHM, the coherent detection is enabled by moving the reference arm at a constant speed, thereby introducing a Doppler frequency shift that leads to spatial interference fringes along the scanning direction. Lastly, we present a unified formulation that treats off-axis and in-line LCHM in a unified joint spatiotemporal modulation framework and provide a connection between LCHM and the traditional off-axis DH. The presented high-speed LCHM may find applications in optical metrology and biomedical imaging.

Coherent artifact suppression in line-field reflection confocal microscopy using a low spatial coherence light source.

Line-field reflection confocal microscopy (LF-RCM) has the potential to add a dimension of parallelization to traditional confocal microscopy while reducing the need for two-axis beam scanning. LF-RCM systems often employ light sources with a high degree of spatial coherence. This high degree of spatial coherence potentially leads to unwanted coherent artifact in the setting of nontrivial sample scattering. Here, we (a) confirm that a coherent artifact is a nontrivial problem in LF-RCM when using spatially coherent light, and (b) demonstrate that such a coherent artifact can be mitigated through the use of reduced spatial coherence line-field sources. We demonstrate coherent noise suppression in a full-pupil line-field confocal microscope using a large number of mutually incoherent emitters from a vertical-cavity surface-emitting lasers (VCSEL) array. The coherent noise from a highly scattering sample is significantly suppressed by the use of this synthesized reduced spatial coherence light source compared to a fully coherent light source. Lastly, with scattering samples, the axial confocality of line-field confocal microscopy is compromised independent of the source spatial coherence, as demonstrated by our experimental result. Our results highlight the importance of spatial coherence engineering in parallelized reflection confocal microscopy.

Feasibility of bioleaching combined with Fenton oxidation to improve sewage sludge dewaterability.

A novel joint method of bioleaching with Fenton oxidation was applied to condition sewage sludge. The specific resistance to filtration (SRF) and moisture of sludge cake (MSC) were adopted to evaluate the improvement of sludge dewaterability. After 2-day bioleaching, the sludge pH dropped to about 2.5 which satisfied the acidic condition for Fenton oxidation. Meanwhile, the SRF declined from 6.45×10(10) to 2.07×10(10) s2/g, and MSC decreased from 91.42% to 87.66%. The bioleached sludge was further conditioned with Fenton oxidation. From an economical point of view, the optimal dosages of H2O2 and Fe2+ were 0.12 and 0.036 mol/L, respectively, and the optimal reaction time was 60 min. Under optimal conditions, SRF, volatile solids reduction, and MSC were 3.43×10(8) s2/g, 36.93%, and 79.58%, respectively. The stability and settleability of sewage sludge were both improved significantly. Besides, the results indicated that bioleaching-Fenton oxidation was more efficient in dewatering the sewage sludge than traditional Fenton oxidation. The sludge conditioning mechanisms by bioleaching-Fenton oxidation might mainly include the flocculation effects and the releases of extracellular polymeric substances-bound water and intercellular water.

Quantitative phase-contrast confocal microscope.

We present a quantitative phase-contrast confocal microscope (QPCCM) by combining a line-scanning confocal system with digital holography (DH). This combination can merge the merits of these two different imaging modalities. High-contrast intensity images with low coherent noise, and the optical sectioning capability are made available due to the confocality. Phase profiles of the samples become accessible thanks to DH. QPCCM is able to quantitatively measure the phase variations of optical sections of the opaque samples and has the potential to take high-quality intensity and phase images of non-opaque samples such as many biological samples. Because each line scan is recorded by a hologram that may contain the optical aberrations of the system, it opens avenues for a variety of numerical aberration compensation methods and development of full digital adaptive optics confocal system to emulate current hardware-based adaptive optics system for biomedical imaging, especially ophthalmic imaging. Preliminary experiments with a microscope objective of NA 0.65 and 40 × on opaque samples are presented to demonstrate this idea. The measured lateral and axial resolutions of the intensity images from the current system are ~0.64µm and ~2.70µm respectively. The noise level of the phase profile by QPCCM is ~2.4nm which is better than the result by DH.

Phase aberration correction by correlation in digital holographic adaptive optics.

We present a phase aberration correction method based on the correlation between the complex full-field and guide-star holograms in the context of digital holographic adaptive optics (DHAO). Removal of a global quadratic phase term before the correlation operation plays an important role in the correction. Correlation operation can remove the phase aberration at the entrance pupil plane and automatically refocus the corrected optical field. Except for the assumption that most aberrations lie at or close to the entrance pupil, the presented method does not impose any other constraints on the optical systems. Thus, it greatly enhances the flexibility of the optical design for DHAO systems in vision science and microscopy. Theoretical studies show that the previously proposed Fourier transform DHAO (FTDHAO) is just a special case of this general correction method, where the global quadratic phase term and a defocus term disappear. Hence, this correction method realizes the generalization of FTDHAO into arbitrary DHAO systems. The effectiveness and robustness of this method are demonstrated by simulations and experiments.

[Effect of Erigeron Breviscapus on the expression of OPG/RANKL/RANK in osteoblasts and pre-osteoclasts in vitro].

OBJECTIVE: To study the effect of Erigeron Breviscapus (EB) at different concentrations and different intervention time points on the mRNA and protein expression of OPG/RANKL/RANK in MG63 osteoblast-like cells and RAW264. 7 pre-osteoclast cells cultured in vitro, thus exploring roles EB played in bone rebuilding and its mechanisms. METHODS: MG63 osteoblast-like cells and RAW264.7 pre-osteoclast cells were cultured in vitro. The 3rd passage cells were divided into the control group and different experimental groups. Total RNA and protein were respectively isolated from cells treated with different concentrations of EB (0, 0.001, 0.01, 0.1, and 1.0 mg/mL) for 48 h. Meanwhile, the protein was extracted from 0 and 1 mg/mL EB groups at 12, 24, and 48 h respectively. Expression of OPG mRNA and RANKL mRNA in MG63 osteoblast-like cells, and expression of RANK mRNA in RAW264.7 pre-osteoclast cells were detected by semi-quantitative RT-PCR. Expression of OPG protein and RANKL protein in MG63 osteoblast-like cells, and expression of RANK protein in RAW264. 7 pre-osteoclast cells were detected by Western blot. RESULTS: Along with increased EB concentration, expression of OPG mRNA and protein in MG63 osteoblast-like cells was gradually lowered (P < 0.05) after 48-h intervention of EB, the expression of RANKL mRNA and protein in MG63 osteoblast-like gradually increased (P < 0.05); the expression of RANK mRNA in RAW264.7 pre-osteoclast cells increased (P < 0.05). But the expression of RANK mRNA was slightly lower in the 0.1 mg/mL EB group than in the 0.01 mg/mL EB group, and the expression of RANK protein in RAW264.7 pre-osteoclast cells gradually increased (P < 0.05). After treatment with 1 mg/mL EB for 12, 24, 48 h, the expression of OPG protein in MG63 osteoblast-like cells gradually decreased as time went by (P < 0.05), and the expression of RANKL protein in MG63 osteoblast-like and RANK protein in RAW264.7 pre-osteoclast cells gradually increased (P < 0.05). The expression of RANKL protein in RAW264.7 pre-osteoclast cells increased as time went by (P < 0.05). CONCLUSION: EB could inhibit the expression of OPG in osteoblasts in a dose- and time-dependent manner, promote the expression of RANKL in osteoblasts and the secretion of RANK in pre-osteoclast, indicating EB might play roles in promoting bone resorption.

siRNA Mediated Downregulation of RhoA Expression Reduces Oxidative Induced Apoptosis in Retinal Ganglion Cells.

BACKGROUNDS: Glaucoma is the second leading cause of blindness. Apoptosis of retinal ganglion cells (RGCs) is an important mechanism of glaucomatous optic injury. Rho kinase expression is significantly increased in apoptotic RGCs. This study aimed to investigate the role of RhoA, a Rho GTPase, on the survival of RGCs and further to explore its potential therapeutic applications. METHODS: RGCs were treated with siRhoA for 24 hours in vitro. Knockdown of RhoA was confirmed with quantitative RT-PCR. Oxidative stress was induced by treating the RGCs with 200 µM of H2O2 for 1 hour, and apoptosis of RGCs was quantified with TUNEL assay in situ, and with flow cytometry. The mRNA expression levels of RhoA, Nogo receptor, caspase 3 and Bcl-2 were evaluated by quantitative RT-PCR, and the protein levels of RhoA, ROCK1, ROCK2, Nogo receptor, caspase 3 and Bcl-2 were evaluated by Western blot. We found siRhoA treatment efficiently downregulated the expression of RhoA in RGCs and protected against H2O2-induced injury in RGCs in vitro. Apoptosis of RGC cells under oxidative stress was quantified in situ using TUNEL assay and confirmed with flow cytometry (FCM). RESULTS: With the knockdown of RhoA, the expression of ROCK1, ROCK2, Nogo Receptor, Casepase-3 were decreased, while the expression of Bcl-2 was increased in both mRNA and protein level. Our data indicated that siRhoA prevented H2O2-induced apoptosis in RGC cells by modulating the RhoA/ROCK pathway. CONCLUSION: The results suggested that siRhoA may exert potentially effective neuroprotection for RGCs by reducing injury.