[Characteristics and Cause of PM2.5 During Haze Pollution in Winter 2022 in Zhoukou, China].

The characteristics and main factors of causes of haze in Zhoukou in January 2022 were analyzed. Six air pollutants, water-soluble ions, elements, OC, EC, and other parameters in fine particulate matter were monitored and analyzed using a set of online high-time-resolution instruments in an urban area. The results showed that the secondary inorganic aerosols(SNA), carbonaceous aerosols(CA, including organic carbon OC and inorganic carbon EC), and reconstructed crustal materials(CM, such as Al2O3, SiO2, CaO, and Fe2O3, etc.) were the three main components, accounting for 61.3%, 24.3%, and 9.72% in PM2.5, respectively. The concentrations of SNA, CA, CM, and SOA were increased, accompanied with higher AQI. The sulfur oxidation rate(SOR) and nitrogen oxidation rate(NOR) in January were 0.53 and 0.46, respectively. The growth rates[µg·(m3·h)] of sulfate and nitrate were 0.027(-5.89-9.47, range) and 0.051(-23.1-12.4), respectively. During the haze period, the growth rates of sulfate and nitrate were 0.13 µg·(m3·h)-1and 0.24 µg·(m3·h)-1, which were 4.8 and 4.7 times higher than the average value of January, respectively. Although the sulfur oxidation rate was greater than the nitrogen oxidation rate, the growth rate of nitrate was approximately 1.8 times that of sulfate owing to the difference in the concentration of gaseous precursors and the influence of relative humidity. The growth rates of nitrate in SNA were significantly higher than those of sulfate on heavily polluted days. The values of SOR, NOR, and concentrations of SNA and SOA during higher AQI and humidity periods were higher than those in lower AQI and humidity periods. The Ox(NO2+O3) decreased with the increase in relative humidity. The SOA was higher at nighttime, increasing faster with the humidity than that in daytime. Under the situation of lower temperature, higher humidity, and lower wind speed, the emission of gaseous precursors of SNA requires further attention in Zhoukou in winter. Advanced control strategies of emissions of SO2 and NO2, such as mobile sources and coal-burning sources, could reduce the peak of haze in winter efficiently.

[Transport Influence and Potential Sources of PM2.5 Pollution for Nanjing].

In this study, 24-hour backward trajectories of the air mass in Nanjing were calculated by using the HYSPLIT model with the NCEP global reanalysis data from March 2019 to February 2020. The backward trajectories combined with the hourly concentration data of PM2.5 were then utilized in the trajectory clustering analysis and potential pollution source analysis. The results showed that the average concentration of PM2.5 in Nanjing was(36±20) µg·m-3 during the study period, with 17 days exceeding the grade Ⅱ national ambient air quality standards (75 µg·m-3). PM2.5 concentration exhibited clear seasonal variation, with winter (49 µg·m-3)>spring (42 µg·m-3)>autumn (31 µg·m-3)>summer (24 µg·m-3). PM2.5 concentration was significantly positively correlated with surface air pressure but significantly negatively correlated with air temperature, relative humidity, precipitation, and wind speed. Based on the trajectories, seven transport routes were identified in spring, and six routes for the other seasons. The northwest and south-southeast routes in spring, southeast route in autumn, and southwest route in winter were the main pollution transport routes in each season, with the characteristics of short transport distance and slow air mass movement, indicating that local accumulation was one of the main reasons for the high value of PM2.5 in quiet and stable weather. The distance of the northwest route in winter was large, and the PM2.5 concentration was 58 µg·m-3, which was the 2nd highest concentration in all routes, indicating that the cities in the northeast of Anhui had a great transport influence on Nanjing PM2.5. The distribution of PSCF and CWT was relatively consistent, and the main potential source areas were mainly local and adjacent areas of Nanjing, indicating that PM2.5 control is needed to strengthen local control and carry out joint prevention and control with adjacent areas. Winter was most affected by transport, its main potential source area was located at the junction of northwest Nanjing and Chuzhou, and the main source origin was in Chuzhou; therefore joint prevention and control should be expanded to Anhui.

Parkin-mediated mitophagy protects against TNF-α-induced stress in bone marrow mesenchymal stem cells.

Bone marrow mesenchymal stem cells (BMSCs) have been investigated as cellular therapeutics for intervertebral disc degeneration. However, transplanted BMSCs are prone to be damaged. TNF-α is reported to extensively promote degeneration process. Nevertheless, the relationship between BMSCs senescence and TNF-α-induced stress has not been elucidated. Previous studies showed that mitophagy is a crucial factor in maintaining cellular homeostasis. Hence, we sought to clarify the role and mechanism of mitophagy in TNF-α-induced biological changes of BMSCs. Here, we found that TNF-α caused transient senescent damage in the early stage. Meanwhile, Parkin-mediated mitophagy was initiated and weakened the damage through maintaining mitochondria homeostasis. After inhibiting mitophagy by knockdown of Parkin, TNF-α irreversibly caused cellular senescence. These results suggested that Parkin-mediated mitophagy played protective role in BMSCs in response to TNF-α, which could be a crucial therapeutic target in the future.

lncRNA-KCNQ1OT1: A Potential Target in Exosomes Derived from Adipose-Derived Stem Cells for the Treatment of Osteoporosis.

BACKGROUND: Osteoporosis is a worldwide medical and socioeconomic burden characterized by systemic impairment of bone strength and microstructure. Exosomes derived from adipose-derived stem cells (ADSCs-Exos) have been confirmed to play effective roles in the repair of various tissues and organs. This study was aimed at investigating the role of ADSCs-Exos and a novel long noncoding RNA KCNQ1OT1 played in osteoporosis as well as the underlying mechanism. METHODS: Primary osteoblasts were treated with different doses of tumor necrosis factor-α (TNF-α) (0, 1, 2.5, 5, and 10 ng/ml) and then cocultured with ADSCs-Exos or exosome-derived from lnc-KCNQ1OT1-modified ADSCs (KCNQ1OT1-Exos). The expression of miRNA-141-5p (miR-141-5p) and lnc-KCNQ1OT1 was evaluated by quantitative real-time polymerase chain reaction (qRT-PCR). The protein expression of cleaved-caspase-3, caspase-3, and Bax was determined by Western blot. Cell viability and apoptosis were assessed by Cell Counting Kit-8 (CCK-8) and flow cytometry analysis, respectively. The binding sites between KCNQ1OT1 and miR-141-5p were validated by dual-luciferase reporter assay. RESULTS: TNF-α dose-dependently increased miR-141-5p expression, inhibited viability, and promoted apoptosis of osteoblasts. However, miR-141-5p silencing or cocultured with ADSCs-Exos attenuated these effects. In addition, KCNQ1OT1-Exos could more significantly attenuate the induced cytotoxicity and apoptosis compared to ADSCs-Exos. Moreover, miR-141-5p was confirmed as the target of KCNQ1OT1 by luciferase reporter assay. CONCLUSIONS: ADSCs-Exos can attenuate cytotoxicity and apoptosis of TNF-α-induced primary osteoblasts. KCNQ1OT1-Exos have a more significant inhibitory effect compared to ADSCs-Exos by the function of sponging miR-141-5p, suggesting that KCNQ1OT1-Exos can be promising agents in osteoporosis treatment.

[Audit Indicators and Suggested Ranges for Data Validation of Chemical Components in Ambient PM2.5: A Case Study of the Yangtze River Delta].

Diagnostic indicators for the validation of PM2.5 compositional data were calculated, based on the monitoring results of approximately 2100 ambient samples collected in the Yangzi River Delta from 2014 to 2017. According to the results of a correlation analysis, we propose that the audit indexes of the monitoring data of PM2.5 components in ambient air should include:equivalent ratios of anion-cation charge balance(A/C), the consistency between sum of all measured components(∑species) and weighed PM2.5, the consistency between mass reconstructed PM2.5(PM2.5, reconstructed) and weighed PM2.5, the chemical consistency between elemental S and water-soluble SO42-, elemental K and water-soluble K+, and the chemical consistency of theoretical and tested NH4+. The double-sided 95% reference ranges of anion-cation equivalent balance (A/C), ∑species/PM2.5, PM2.5, reconstructed/PM2.5, S/SO42-, and K/K+ ratios were determined in terms of P2.5 and P97.5 as follows:(0.82, 1.35), (0.63, 0.94), (0.62, 1.00), (0.28, 0.50), and (0.66, 2.31). These diagnostic indicators were helpful for judging the errors of chemical component analysis and retain seasonal variation stability. In most cases, NH4+ existed in the form of NH4NO3 and (NH4)2SO4 in spring and summer. With the approach of autumn and winter, it transformed to NH4NO3, (NH4)2SO4, and NH4Cl. The results of literature verification showed the pass rate of A/C was 87.1% and the rate of other indexes was 100%, indicating that the above audit indexes we propose could be applied to not only the Yangzi River Delta but the entire country. Furthermore, there were certain conditions in applying the diagnostic indicators. The S/SO42- ratio worked well with PM2.5 ≥ 40 µg·m-3 in summer and with 60 µg·m-3 ≤ PM2.5 ≤ 140 µg·m-3 in spring, autumn, and winter. Other audit indexes were available universally in all weathers under the condition of PM2.5 ≥ 60 µg·m-3.

Bifunctional Carbenium Dications as Metal-Free Catalysts for the Reduction of Oxygen.

The development of catalysts for the oxygen reduction reaction is a coveted objective of relevance to energy research. This study describes a metal-free approach to catalyzing the reduction of O2 into H2O2, based on the use of redox-active carbenium species. The most active catalysts uncovered by these studies are the bifunctional dications 1,8-bis(xanthylium)-biphenylene ([3]2+) and 4,5-bis(xanthylium)-9,9-dimethylxanthene ([4]2+) which promote the reaction when in the presence of decamethylferrocene and methanesulfonic acid. Electrochemical studies carried out with [4]2+ suggest the intermediacy of an organic peroxide that, upon protonation, converts back into the starting dication while also releasing H2O2. Kinetic studies point to the second protonation event as being rate-determining.

Mitophagy is a protective response against oxidative damage in bone marrow mesenchymal stem cells.

AIMS: Bone marrow mesenchymal stem cells (BMSCs) show great potential in clinical applications such as in intervertebral disc degeneration. Nevertheless, environmental stress during the BMSC transplant or in the injured tissues is a catastrophic factor that causes cell toxicity and poor survival of BMSCs. Mitophagy plays a vital role in maintaining cellular homeostasis and defending against oxidative stress because this process could control mitochondrial quality and quantity by eliminating dysfunctional or damaged mitochondria that can cause cell death. However, the accurate mechanisms of mitophagy in protecting BMSCs against the harshness of oxidative stress remain largely unknown. MAIN METHODS: BMSCs were treated with H2O2 for various time periods. Mitophagy response was evaluated through the expression levels of LC3-II, p62 and mitophagosomal formation by using Western blot and fluorescence analysis. Cell apoptosis was examined by flow cytometry and TUNEL assay. The interactions of mitophagy and apoptosis and the possible signalling pathways were investigated through the co-treatment of mitophagy inhibitor or mitophagy activator with H2O2. KEY FINDINGS: Oxidative stress rapidly facilitated mitophagy through JNK at an early stage but decreased mitophagy and increased apoptosis at a late stage. Furthermore, mitophagy inhibition significantly enhanced the apoptosis in the cells treated by H2O2. SIGNIFICANCE: Induced mitophagy may play pivotal roles in protecting cells against oxidative stress in BMSCs.

Molecular Regulation Mechanisms and Interactions Between Reactive Oxygen Species and Mitophagy.

The generation of reactive oxygen species (ROS) in response to oxidative stress has important effects on cell development, normal function, and survival. It may cause oxidative damage to intracellular macromolecular substances and mitochondria through several signaling pathways. However, the damaged mitochondria promote further ROS generation, creating a vicious cycle that can cause cellular injury. In addition, excessive ROS produced by damaged mitochondria can trigger mitophagy, a process that can scavenge impaired mitochondria and reduce ROS level to maintain stable mitochondrial function in cells. Therefore, mitophagy heaps maintain cellular homeostasis under oxidative stress. In this article, we review recent advances in cellular damage caused by excessive ROS, the mechanism of mitophagy, and the close relationship between ROS and mitophagy. This review provides a new perspective on therapeutic strategies for related diseases.

Coordination of a stibine oxide to a Lewis acidic stiborane at the upper rim of the biphenylene backbone.

Our interest in bifunctional antimony Lewis acids has led us to synthesize 1,8-bis(diphenylstibino)biphenylene (2) by reaction of 1,8-bis(trimethylstannyl)biphenylene (1) with Ph2SbCl. Oxidation of this distibine with o-chloranil, followed by work-up in air afforded a biphenylene derivative (3) featuring a triarylstibine oxide connected via an Sb[double bond, length as m-dash]O → Sb bridge to the neighbouring antimony(v) center.

Digging the Sigma-Hole of Organoantimony Lewis Acids by Oxidation.

The development of group 15 Lewis acids is an area of active investigation that has led to numerous advances in anion sensing and catalysis. While phosphorus has drawn considerable attention, emerging research shows that organoantimony(III) reagents may also act as potent Lewis acids. Comparison of the properties of SbPh3 , Sb(C6 F5 )3 , and SbArF 3 with those of their tetrachlorocatecholate analogues SbPh3 Cat, Sb(C6 F5 )3 Cat, and SbArF 3 Cat (Cat=o-O2 C6 Cl4 , ArF =3,5-(CF3 )2 C6 H3 ) demonstrates that the Lewis acidity of electron deficient organoantimony(III) reagents can be readily enhanced by oxidation to the +V state-as verified by binding studies, organic reaction catalysis, and computational studies. The results are rationalized by explaining that oxidation of the antimony center leads to a lowering of the accepting σ* orbital and a deeper carving of the associated σ-hole.

Large-bite diboranes for the µ(1,2) complexation of hydrazine and cyanide.

As part of our interest in the chemistry of polydentate Lewis acids as hosts for diatomic molecules, we have investigated the synthesis and coordination chemistry of bidentate boranes that feature a large boron-boron separation. In this paper, we describe the synthesis of a new example of such a diborane, namely 1,8-bis(dimesitylboryl)triptycene (2) and compare its properties to those of the recently reported 1,8-bis(dimesitylboryl)biphenylene (1). These comparative studies reveal that these two diboranes feature some important differences. As indicated by cyclic voltammetry, 1 is more electron deficient than 2; it also adopts a more compact and rigid structure with a boron-boron separation (4.566(5) Å) shorter by ∼1 Å than that in 2 (5.559(4) Å). These differences appear to dictate the coordination behaviour of these two compounds. While 2 remains inert toward hydrazine, we observed that 1 forms a very stable µ(1,2) hydrazine complex which can also be obtained by phase transfer upon layering a solution of 1 with a dilute aqueous hydrazine solution. The stability of this complex is further reflected by its lack of reaction with benzaldehyde at room temperature. We have also investigated the behaviour of 1 and 2 toward anions. In MeOH/CHCl3 (1/1 vol) both compounds selectively bind cyanide to form the corresponding µ(1,2) chelate complexes with a B-C[triple bond, length as m-dash]N-B bridge at their cores. Competition experiments in protic media show that the anionic cyanide complex formed by 1 is the most stable, with no evidence of decomplexation even in the presence of (C6F5)3B.

[Estimation of Fine Particle (PM2.5) Emission Inventory from Cooking: Case Study for Shanghai].

Cooking is one of important emission sources of fine particles (PM2.5). This study using the catering enterprises of Shanghai as an example, presents a method to estimate the PM2.5 emission inventory from cooking according to the number of stoves, cooking time, and number of customers. Based on in situ measurements, the concentrations of PM2.5 emissions ranged from 0.1 mg ·m-3 to 1.8 mg ·m-3, which exceeded the limit (1.0 mg ·m-3 for lampblack) in the national standard. Organic carbon dominated the PM2.5 emitted from cooking, accounting for more than 50%. Extremely high ratios of organic carbon to elemental carbon were observed, ranging from 58.8 to 752.3, which could be used as an indicator of cooking emissions. The emission factors of PM2.5 in the catering industry are closely related to the scale of the catering enterprises. The emission factors of large-and medium-sized enterprises are obviously higher than those of small and micro enterprises. The PM2.5 emissions of catering enterprises are mainly attributed to high emission loads of large enterprises and those for a large number of small and medium enterprises. The PM2.5 emission inventory of cooking in Shanghai was calculated according to the three emission factors above, and the results were very close. Therefore, the method for estimating the PM2.5 emission inventory for cooking presented in this study is helpful for other Chinese cities to calculate their PM2.5 emission inventory from cooking.

[Chemical Characterization, Spatial Distribution, and Source Identification of Organic Matter in PM2.5 in summertime Shanghai, China].

Particulate organic matter (POM) has attracted increasing attention recently due to its great contribution to fine particles (PM2.5) and complex components and sources. In the present study, 78 particulate organic compounds in PM2.5 were quantified at three sites in Shanghai during summer; these sites were located in urban (Xuhui), suburban (Qingpu), and coastal (Lin'gang) areas of the city. Accordingly, the chemical composition and spatial distribution were investigated and sources were explored based on the indicators and diagnostic ratios combined with backward trajectory. The results showed that during the period of observation, the quantified organic matter in the suburban area is about 319 ng ·m-3, close to the urban area but much higher than that of the coastal areas. Fatty acids were the largest contributors, followed by levoglucosan, polycyclic aromatic hydrocarbons (PAHs), n-alkanes, and hopanes. Source analysis based on tracer methods indicates that gasoline vehicle emissions were the main source of POM in Shanghai. Biomass burning from the northeast impacted somewhat on the urban area and western suburbs during the observation period. Terrestrial plant emissions played an important role in the source of fatty acids at Qingpu and Lin'gang, and emissions of marine phytoplankton and microorganisms were also important for fatty acids at Lin'gang. Coal combustion and motor vehicle exhaust made an important contribution to PAHs according to an analysis of diagnostic ratios. This study presented the characteristics and sources of POM in summertime Shanghai, which facilitates the development of an effective control strategy on PM2.5 pollution.

Exploiting the Strong Hydrogen Bond Donor Properties of a Borinic Acid Functionality for Fluoride Anion Recognition.

Borinic acids have typically not been considered as hydrogen bond donor groups in molecular recognition. Described herein is a bifunctional borane/borinic acid derivative (2) in which the two functionalities are connected by a 1,8-biphenylenediyl backbone. Anion binding studies reveal that 2 readily binds a fluoride anion by formation of a unique B-F⋅⋅⋅H-O-B hydrogen bond. This hydrogen bond is characterized by a short H-F distance of 1.79(3) Šand a large coupling constant (1 JHF ) of 57.2 Hz. The magnitude of this interaction, which has also been investigated computationally, augments the fluoride anion binding properties of 2, thus making it compatible with aqueous environments.

Fluoride Anion Complexation by a Triptycene-Based Distiborane: Taking Advantage of a Weak but Observable C-H⋠⋠⋠F Interaction.

Fluoride anion complexation impacts a number of areas ranging from sensing to nucleophilic fluorination chemistry. Described here is a new bidentate Lewis acid consisting of two stiborane units connected by a 1,8-triptycenediyl backbone. This neutral derivative captures fluoride with an unprecedented affinity for a neutral, water-compatible Lewis acid. Structural, spectroscopic and computational studies demonstrate that fluoride anion binding is assisted by the formation of a C-H⋅⋅⋅F hydrogen bond which involves a methine group of the 1,8-triptycenediyl backbone.

Correction: Synthesis of N-heterocyclic carbene rhenium(i) carbonyl complexes.

Correction for 'Synthesis of N-heterocyclic carbene rhenium(i) carbonyl complexes' by Chang-Hong Chen, et al., Dalton Trans., 2012, 41, 2747-2754.

[Chemical Characteristics of Particulate Matters and Trajectory Influence on Air Quality in Shanghai During the Heavy Haze Episode in December, 2013].

Intensive haze shrouded central and eastern parts of China in Dec. 2013. In this study, the mass concentrations of gaseous and particulate pollutants, and also the chemical compositions of fine particulate matters were obtained based on in-situ measurement in Shanghai urban area. The characteristics of PM2.5 were investigated during different pollution episodes, including dust, haze, fog-haze and long-rang transport episodes. The results showed that pollution was most serious during the fog-haze episode, during which the maximum daily mass concentrations of PM10 and PM2.5 reached 536 microg x m(-3) and 411 microg x m(-3), respectively. During the fog-haze episode, the ratio of PM2.5 to PM10 was over 76.7%, suggesting that high humidity enhanced the secondary formation of NO3-, SO4(2-) and NH4+ in PM2.5. Highest concentration of Ca2+ in PM2.5 occurred during the dust episode and the proportion of primary components in PM2.5 increased obviously. Highest concentration of SO2- was observed in PM25 during the long-range transport episode, with a fast growth rate. Meanwhile, the trajectories reaching Shanghai urban area and cluster analysis during different pollution episodes were simulated by HYSPLIT model. Combined with observation data of PM2.5 in Shanghai urban area, chemical characteristics of PM2.5 in different clusters and potential source apportionment of various pollution episodes were also studied in this study. The result revealed that the air trajectories could be grouped into six clusters based on their spatial similarities. Among these clusters, cluster6 which moved fast was associated with clean air. Cluster2 and cluster3 originating from Mongolia region had strong correlations to dust pollution, along with low PM2.5/PM10 ratio and high concentration of Ca2+ in PM2.5. Compared with other clusters, cluster5 and cluster4 with slow moving speed were more favorable for reactions between particulate species and formation of secondary pollutants during transport. Additionally, the stagnant weather condition under these two clusters with high water vapor when passing over the East China Sea further led to the aggravation of atmospheric pollution in Shanghai.

Efficacy of volar and dorsal plate fixation for unstable dorsal distal radius fractures.

OBJECTIVE: To compare the efficacy of volar and dorsal plate fixation for unstable dorsal distal radius fractures. METHODS: Forty-seven cases were selected from patients undergoing surgical reduction and internal fixation treatment in our hospital from August 2006 to October 2010, with 21 males and 26 females, aged 39-73 years old. Patients were divided into two groups: volar plate fixation group (Group A) which has 32 cases, including 27 cases with locking plate, 5 cases with ordinary T plate, and 4 cases combined with dorsal Kirschner wire fixation; dorsal plate fixation group (Group B) which has 15 cases, including 7 cases with locking plate. The efficacy of the two fixation methods were compared in terms of postoperative wrist function, X-ray score, and postoperative complications. RESULTS: Compared with those of preoperative groups, the volar tilt, ulnar deviation and radial styloid height in both group A and B were significantly improved one week after surgery as shown by X-ray imaging. Comparison of X-ray images one week after surgery with those of six months after surgery showed no significant changes in volar tilt, ulnar deviation or radial styloid height. 87.5% of patients in group A and 86.7% of patients in group B got "excellent" in their wrist function assessment, and there was no significant difference between the two groups (X(2)=0.825, P=1.000). But patients in group A hax significantly lower incidence rate of postoperative complications than group B (X(2)=4.150, P=0.042). CONCLUSION: For unstable distal radius fractures with dorsal displacement, volar plate fixation can achieve satisfactory reduction results, and cause less tendon damage or other complications than dorsal plate fixation.

Effects of hook plate on shoulder function after treatment of acromioclavicular joint dislocation.

INTRODUCTION: Internal fixation with hook plate has been used to treat acromioclavicular joint dislocation. This study aims to evaluate the effect of its use on shoulder function, to further analyze the contributing factors, and provide a basis for selection and design of improved internal fixation treatment of the acromioclavicular joint dislocation in the future. METHODS: A retrospective analysis was performed on patients treated with a hook plate for acromioclavicular joint dislocation in our hospital from January 2010 to February 2013. There were 33 cases in total, including 25 males and 8 females, with mean age of 48.27 ± 8.7 years. There were 29 cases of Rockwood type III acromioclavicular dislocation, 4 cases of type V. The Constant-Murley shoulder function scoring system was used to evaluate the shoulder function recovery status after surgery. Anteroposterior shoulder X-ray was used to assess the position of the hook plate, status of acromioclavicular joint reduction and the occurrence of postoperative complications. RESULTS: According to the Constant-Murley shoulder function scoring system, the average scores were 78 ± 6 points 8 to 12 months after the surgery and before the removal of the hook plate, the average scores were 89 ± 5 minutes two months after the removal of hook plate. Postoperative X-ray imaging showed osteolysis in 10 cases (30.3%), osteoarthritis in six cases (18.1%), osteolysis associated with osteoarthritis in four cases(12.1%), and steel hook broken in one case (3%). CONCLUSION: The use of hook plate on open reduction and internal fixation of the acromioclavicular joint dislocation had little adverse effect on shoulder function and is an effective method for the treatment of acromioclavicular joint dislocation. Osteoarthritis and osteolysis are the two common complications after hook plate use, which are associated with the impairment of shoulder function. Shoulder function will be improved after removal of the hook plate.