Abstract. In 2013, China's government published the Air Pollution Prevention and Control Action Plan (APPCAP) with a specific target for Beijing, which aims to reduce annual mean PM2.5 concentrations in Beijing to 60 µg m−3 in 2017. During 2013–2017, the air quality in Beijing was significantly improved following the implementation of various emission control measures locally and regionally, with the annual mean PM2.5 concentration decreasing from 89.5 µg m−3 in 2013 to 58 µg m−3 in 2017. As meteorological conditions were more favourable to the reduction of air pollution in 2017 than in 2013 and 2016, the real effectiveness of emission control measures on the improvement of air quality in Beijing has frequently been questioned. In this work, by combining a detailed bottom-up emission inventory over Beijing, the MEIC regional emission inventory and the WRF-CMAQ (Weather Research and Forecasting Model and Community Multiscale Air Quality) model, we attribute the improvement in Beijing's PM2.5 air quality in 2017 (compared to 2013 and 2016) to the following factors: changes in meteorological conditions, reduction of emissions from surrounding regions, and seven specific categories of local emission control measures in Beijing. We collect and summarize data related to 32 detailed control measures implemented during 2013–2017, quantify the emission reductions associated with each measure using the bottom-up local emission inventory in 2013, aggregate the measures into seven categories, and conduct a series of CMAQ simulations to quantify the contribution of different factors to the PM2.5 changes. We found that, although changes in meteorological conditions partly explain the improved PM2.5 air quality in Beijing in 2017 compared to 2013 (3.8 µg m−3, 12.1 % of total), the rapid decrease in PM2.5 concentrations in Beijing during 2013–2017 was dominated by local (20.6 µg m−3, 65.4 %) and regional (7.1 µg m−3, 22.5 %) emission reductions. The seven categories of emission control measures, i.e. coal-fired boiler control, clean fuels in the residential sector, optimize industrial structure, fugitive dust control, vehicle emission control, improved end-of-pipe control, and integrated treatment of VOCs, reduced the PM2.5 concentrations in Beijing by 5.9, 5.3, 3.2, 2.3, 1.9, 1.8, and 0.2 µg m−3, respectively, during 2013–2017. We also found that changes in meteorological conditions could explain roughly 30 % of total reduction in PM2.5 concentration during 2016–2017 with more prominent contribution in winter months (November and December). If the meteorological conditions in 2017 had remained the same as those in 2016, the annual mean PM2.5 concentrations would have increased from 58 to 63 µg m−3, exceeding the target established in the APPCAP. Despite the remarkable impacts from meteorological condition changes, local and regional emission reductions still played major roles in the PM2.5 decrease in Beijing during 2016–2017, and clean fuels in the residential sector, coal-fired boiler control, and optimize industrial structure were the three most effective local measures (contributing reductions of 2.1, 1.9, and 1.5 µg m−3, respectively). Our study confirms the effectiveness of clean air actions in Beijing and its surrounding regions and reveals that a new generation of control measures and strengthened regional joint emission control measures should be implemented for continued air quality improvement in Beijing because the major emitting sources have changed since the implementation of the clean air actions.
Metallic zinc is a promising anode material for rechargeable Zn-based batteries. However, the dendritic growth of zinc has prevented practical applications. Herein it is demonstrated that dendrite-free zinc deposits with a nanocrystalline structure can be obtained by using nickel triflate as an additive in a zinc triflate containing ionic liquid. The formation of a thin layer of Zn-Ni alloy (η- and γ-phases) on the surface and in the initial stages of deposition along with the formation of an interfacial layer on the electrode strongly affect the nucleation and growth of zinc. A well-defined and uniform nanocrystalline zinc deposit with particle sizes of about 25 nm was obtained in the presence of Ni(II) . Further, it is shown that the nanocrystalline Zn exhibits a high cycling stability even after 50 deposition/stripping cycles. This strategy of introducing an inorganic metal salt in ionic liquid electrolytes can be considered as an efficient way to obtain dendrite-free zinc.
Ionic liquids are potential designer electrolytes for energy storage devices such as batteries and capacitors wherein by changing the cation and anion of the ionic liquid (IL) the solid/liquid interface can be tuned, thereby influencing the charge and mass transfer processes. In this paper, we show the influence of water on the electrified ionic liquid 1-ethyl-3-methylimidazolium trifluoromethylsulfonate ([Emim]TfO)/Au(111) interface using in situ atomic force microscopy (AFM) and spectroscopy. A clear “water in IL” to “IL in water” transition could be observed in the range of 20–30 vol % of water using vibrational spectroscopy. Above 30 vol % of water the cation–anion interaction in the ionic liquid drastically reduced, which was ascertained by both spectroscopy and interfacial studies using in situ AFM. In situ AFM results further revealed that the structure of the innermost (Stern) layer depends both on the applied electrode potential and the amount of added water. A transition from a multilayered structure to a classical double-layered structure occurred at −1.0 V on changing the water concentration from 30 to 50 vol %. Furthermore, the morphology of the electrodeposited Zn could be altered with addition of water to the electrolyte which has some potential for Zn-based batteries.
The HPLC retention time, photodiode array UV spectrum analysis, and LC/MS results indicated that arbutin and chlorogenic acid are the main phenolic constituents in Oriental pear. The two compounds exist in different organs of the Yali pear, which is one of the major cultivars of Pyrus bretschnrideri. The contents of arbutin in the leaf bud, floral bud, flower, and young fruit were 11.9, 12.4, 8.29, and 9.92 mg/g fresh weight (FW), respectively. Chlorogenic acid amounts in the same organs were 2.26, 3.22, 5.32, and 3.72 mg/g FW, respectively. During development, the concentration of the two compounds in Yali pears was the greatest in young fruit (9.92 mg/g FW of arbutin and 3.72 mg/g FW of chlorogenic acid), and then declined swiftly with fruit growth to less than 0.400 and 0.226 mg/g FW, respectively, in mature fruit. Large differences existed in the distribution of the two compounds in parts of the mature fruit of 14 Oriental pear cultivars. The greatest concentration of arbutin was found in the peel (1.20 mg/g FW), which was 3-5 times greater than that found in the core and 10-45 times greater than the level in the pulp. The concentration of chlorogenic acid in the core was greater than that in the peel. The compounds in 17 cultivars of Oriental pear, including P. bretschnrideri, Pyrus pyrifolia, Pyrus ussuriensis, and Pyrus sinkiangensis, were compared with those in 5 cultivars of Occidental pear (Pyrus communis). The mean concentration of arbutin in the Oriental pear cultivars was 0.164 mg/g FW, greater than the 0.083 mg/g FW found in the Occidental pear cultivars. The greatest arbutin content was 0.400 mg/g FW, found in the Yali pear. However, the mean concentration of chlorogenic acid in the Oriental pear was 0.163 mg/g FW, less than that found in the Occidental pear (0.309 mg/g FW).
The levels of seven polyphenols (epicatechin, procyanidin B2, procyanidin B5, procyanidin C1, hyperoside, isoquercitrin, and chlorogenic acid) and two triterpene acids (oleanolic acid and ursolic acid) in the matured fruits of Chinese hawthorn (Crataegus pinnatifida Bge. var. major N.E.Br.) were determined by high-performance liquid chromatography methods. The average contents of those constituents in 37 representative cultivars were 1405, 1505, 339, 684, 56, 41, 234, 952, and 147 microg/g fresh weight (FW), respectively. A significant inverse correlation between the procyanidin contents and the latitude of the geographical origin of the cultivars was observed (r = 0.3851, P < 0.02). Correlation analysis of the levels of the nine compounds in the 37 cultivars yielded a strong correlation (P < 0.001) between the individual levels of the four procyanidins and the sum of the procyanidins level (r = 0.7413-0.9898) and between the flavonoids and the chlorogenic acid (r = 0.5383-0.9212). The changes in level of the nine compounds in the hawthorn fruit were evaluated during maturation using the Hebei Dajinxing cultivar. Sixty-one days after blossom, the polyphenol level reached the highest point and the sum of the contents was 1.36 g/100 g FW.
Biomineralization is mediated by extracellular matrix (ECM) proteins with amino acid sequences rich in glutamic acid. The objective of this study was to investigate the effect of calcium phosphate deposition on aligned nanofibres surface-modified with a glutamic acid peptide on osteogenic differentiation of rat marrow stromal cells. Blend of EEGGC peptide (GLU) conjugated low molecular weight polylactide (PLA) and high molecular weight poly(lactide-co-glycolide) (PLGA) was electrospun to form aligned nanofibres (GLU-NF). The GLU-NF microsheets were incubated in a modified simulated body fluid for nucleation of calcium phosphate crystals on the fibre surface. To achieve a high calcium phosphate to fibre ratio, a layer-by-layer approach was used to improve diffusion of calcium and phosphate ions inside the microsheets. Based on dissipative particle dynamics simulation of PLGA/PLA-GLU fibres, > 80% of GLU peptide was localized to the fibre surface. Calcium phosphate to fibre ratios as high as 200%, between those of cancellous (160%) and cortical (310%) bone, was obtained with the layer-by-layer approach. The extent of osteogenic differentiation and mineralization of marrow stromal cells seeded on GLU-NF microsheets was directly related to the amount of calcium phosphate deposition on the fibres prior to cell seeding. Expression of osteogenic markers osteopontin, alkaline phosphatase (ALP), osteocalcin and type 1 collagen increased gradually with calcium phosphate deposition on GLU-NF microsheets. Results demonstrate that surface modification of aligned synthetic nanofibres with EEGGC peptide dramatically affects nucleation and growth of calcium phosphate crystals on the fibres leading to increased osteogenic differentiation of marrow stromal cells and mineralization.
Hawthorn polyphenol (HP) was prepared by ethyl acetate treatment of the ethanol extract (HE) of Chinese hawthorn fruit. The concentrations of 15 polyphenols in the HP, HE, extraction residue (HJ), and a hawthorn leaf extract (HF) were determined by HPLC. For HP, the total content of the 15 polyphenols was 21.4%, comprised of 19.7% of procyanidins, 1.21% of chlorogenic acid, and 0.48% of flavonoids, compared to 2.55% for the HE. The yields of procyanidin monomer, dimer, trimer, tetramer, and pentamer were 50.5%, 30.3%, 23.0%, 14.6%, and 12.5% respectively, and the mean degree of polymerization was reduced to 1.39 (HP) from 1.65 (HE). Seven different physiological actions of the four extracts were investigated. The HP showed strong O 2 À and OH scavenging capacities (IC 50 values of 6.3 g/ml and 1.1 g/ml respectively), as well as selective prolyl endopeptidase inhibition (IC 50 of 60 g/ml). The active constituents appeared to be procyanidins.Key words: Crataegus pinnatifida; HPLC; procyanidin; antioxidant; free radicalsIn Europe, standardized extracts of the leaves and flowers of Crataegus oxyacantha and Crataegus monogyna are used in the therapy for moderate (NYHA II) congestive heart failure. 1,2) These extracts exert several pharmacological and clinical effects, such as antiischemia/reperfusion-injury, anti-arrhythmic, hypolipidemic, and hypotensive effects. 1,2) Flavonoids and procyanidins are considered to be the two main active constituents. 2) Species of Chinese hawthorn, particularly Crataegus pinnatifida and Crataegus pinnatifida Bge. var. major NE Br., have also been used as herbal medicines. 2,3) Studies indicate that Chinese hawthorn extracts have beneficial effects, such as antioxidant, 4,5) anti-inflammatory, 6) and hypolipidemic effects, 7) as well as protective effects on the brain and vascular endothelium 8,9) and endothelium-dependent relaxation. 10) Recently, we analyzed 37 major cultivars of Chinese hawthorn using high performance liquid chromatography (HPLC), and found that procyanidins, which were present in high concentrations, were the main phenolic active constituents in these fruits. 11) In general, the hawthorn found in China is an edible fruit that is popular for its special acidic taste. It is bigger than its European counterpart. Since the content of organic acid in Chinese hawthorn fruits can be up to 5% (fresh weight), they are used to produce various foods, such as jams, jellies, juices, tinned foods, wines, and various sweet foods. However, the high sugar content of these fruits counteracts the benefits of polyphenols for consumers of advanced age or for those who suffer from hypertension, cardiovascular disease, or diabetes. Hence, it is desirable to separate the polyphenol and sugar components. Previously, hawthorn extract (HE) for medical applications were ethanol-extracted from the dried fruit of the Chinese hawthorn. 12) These crude extracts contain many undesirable substances, such as carbohydrates, organic acids, and moisture, which not only reduce the concentration of acti...
The effect of anions on the solid/ionic liquid (IL) interface and the electrodeposition of zinc have been investigated. The employed ILs are composed of 1-ethyl-3-methylimidazolium ([EMIm]+), bis(trifluoromethylsulfonyl)imide (TFSI–), trifluoromethylsulfonate (TfO–), methylsulfonate (OMs–) and acetate (OAc–). These anions show an increasing cation–anion interaction strength in the order TFSI– < TfO– < OMs– < OAc–, as probed by far-infrared spectroscopy below 200 cm–1. It was shown by in situ AFM that the anion has a profound impact on the interfacial properties. Multilayered structures were observed at the electrode/IL interface for [EMIm]TFSI and [EMIm]TfO, respectively, while only a few layers with rather a low push-through force were found at the interface for [EMIm]OMs and [EMIm]OAc, respectively. The coordination of Zn(II) ions in these ILs by varying zinc salts was investigated by Raman spectroscopy. The differences in metal species and interfacial layers have a strong influence on the electrochemical process and on the quality of the deposits. Dense zinc deposits with nanowire-like and hexagonal plate-like structures were obtained from ILs with TFSI– and TfO– anions, respectively. Thin layers of zinc with porous and spongy structures were obtained in ILs with OMs– anion containing 0.2 mol/L zinc salts, while homogeneous and smooth deposits with a fine-grained structure were obtained with 1 mol/L zinc salts. However, no deposits were found in Zn(OAc)2/[EMIm]OAc under the same conditions. These results indicated that the anions of ILs strongly affected the solid/IL interface, the speciation of Zn(II) ions in ILs, and the morphology of zinc deposits.
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